The invention provides an improved BiCMOS device and a method of fabricating such a BiCMOS device which requires fewer process steps than known fabrication methods. In one embodiment, the invention provides a method of forming an interpoly capacitor in a BiCMOS device which maintains the thickness of the interpoly dielectric in the capacitor while a window is etched for the emitter in a bipolar transistor. The method includes the use of a thin polysilicon layer overlying the oxide layer, which protects the oxide from etching while the emitter window is etched.

The present invention relates generally to semiconductor devices, and more specifically to fabrication methods for BiCMOS devices.
BiCMOS devices combine both bipolar and metal oxide semiconductor (MOS) transistors on a single integrated circuit. Bipolar and MOS devices each offer unique performance advantages which, when combined into a single package, produce a device with distinct advantages over either technology by itself. Such advantages are discussed in A. R. Alvarez, BiCMOS Technology and Applications, pp. 1-17, which is incorporated herein by reference.
Known methods for fabricating BiCMOS devices are described in, for example, U.S. Pat. No. 4,764,480 to Vora, U.S. Pat. No. 4,868,135 to Ogura et al. and in A. R. Alvarez, BiCMOS Technology and Applications, pp. 63-119, all of which are incorporated herein by reference for all purposes.
It is frequently desirable to fabricate BiCMOS devices with one or more capacitors formed on the substrate in addition to the bipolar and MOS transistors. Such capacitors commonly consist of a first polysilicon layer, a layer of oxide or other dielectric on the first polysilicon layer, and a second polysilicon layer on the oxide layer. This type of interpoly capacitor is particularly desirable because of its low parasitic capacitance.
A known method for fabricating an interpoly capacitor in a BiCMOS device is described in A. R. Alvarez, supra, at pp. 115-119. Alvarez describes a method wherein a first layer of polysilicon is formed on an oxide region of the substrate to form the capacitor, the same layer of polysilicon being formed on the MOS regions of the substrate to form gate electrodes. An interlevel dielectric (ILD) is formed over the first polysilicon region, using either oxide or oxide/nitride combination. A second polysilicon layer is then formed over the ILD layer to form the second terminal of the capacitor.
It should be noted that the device formed by the method disclosed in Alvarez does not utilize a polysilicon emitter contact for the bipolar transistor. In some advanced BiCMOS fabrication processes, a polysilicon emitter contact is formed over the bipolar base and an emitter diffused from the polysilicon emitter contact. An example of such a process is disclosed in Bastani, "Advanced One Micron BiCMOS Technology For High Speed 256K SRAMs", the full disclosure of which is incorporated herein by reference. Bastani describes a BiCMOS fabrication process wherein an oxide layer forming the interpoly dielectric is formed over the bipolar base. The oxide layer is then etched over a portion of the bipolar base to create an emitter window. A second polysilicon layer is then formed over the oxide layer, including in the emitter window, and the second polysilicon layer is etched to form the emitter contact.
It has been found that in forming a polysilicon emitter contact through an emitter window using a process such as that just described, it is extremely important to ensure the silicon surface of the base region in the emitter window remains free of oxide when the polysilicon layer is formed. Typically, over a short period in an oxygen-containing atmosphere, the silicon surface will tend to grow a thin layer of native oxide. Therefore, just before deposition of the second polysilicon layer, a very short etching step is conducted to remove this native oxide from the emitter window.
This short etching step, however, has led to difficulties when a capacitor like that disclosed in Alvarez is desired on a BiCMOS device with a polysilicon emitter contact like that of Bastani. To form such a device, an oxide layer is formed over the first polysilicon terminal of the capacitor as well as over the bipolar base, allowing both the interpoly dielectric of the capacitor as well as the emitter window to be formed from the same oxide layer. The polysilicon layer used to form the emitter contact may be used also to form the second polysilicon terminal of the capacitor.
However, such a process has suffered from the inability to prevent etching of the oxide layer of the interpoly capacitor during the short etching step to remove native oxide in the emitter opening before deposition of the second polysilicon layer. It is critical that the thickness of the interpoly dielectric be maintained within a certain range in order for the capacitor to perform properly. The etching step for removing the oxide in the emitter window will also tend to remove some oxide needed for the interpoly dielectric, making it difficult to control the interpoly dielectric thickness.
For these reasons, a method of fabricating an interpoly capacitor on a BiCMOS device is desired which allows formation of a polysilicon emitter contact, but which allows etching of the oxide in the emitter window for such a contact while maintaining the thickness of the interpoly dielectric layer for the capacitor. The method should minimize process steps, preferably allowing the same oxide layer used for the interpoly dielectric to be used for forming an emitter window in which the polysilicon emitter contact is formed.


The present invention relates, in general, to gene expression and, in particular, to a method of inhibiting the expression of a target gene and to constructs suitable for use in such a method.

Animal cells have recently been shown to express a novel class of single-stranded, ˜22 nucleotide (nt) non-coding RNAs, termed micro RNAs (miRNAs) (Lagos-Quintana et al, Science 294:853-858 (2001); Lau et al, Science 294:858-862 (2001); Lee and Ambros, Science 294:862-864 (2001)). miRNAs appear to be derived from ˜70 nt precursors that form a predicted RNA stem-loop structure. It remains unclear whether these miRNA precursor molecules are transcribed from autonomous promoters or are instead contained within longer RNAs (Ambros, Cell 107:823-826 (2001); Lau et al, Science 294:858-862 (2001)).
While over 100 distinct miRNAs are expressed in organisms as diverse as nematodes (Lau et al, Science 294:858-862 (2001), Lee et al, Science 294:862-864 (2001)), fruit flies (Lagos-Quintana et al, Science 294 858-858 (2002), and humans (Mourelatos et al, Genes Dev. 16:720-728 (2002)), as well as in plants (Tang et al, Genes Dev. 17:49-63 (2003), Reinhart et al, Genes Dev. 16:1616-1626 (2002)), their function remains largely uncertain. However, the biological activity of two miRNAs, C. elegans let-7 and lin-4, is well established (Lee et al, Cell 75:843-854 (1993); Reinhart et al, Nature 403:901-906 (2000)). Both lin-4 and let-7 are expressed during specific larval stages and both miRNAs interact with partially complementary RNA targets, located in the 3′ untranslated region (3′ UTR) of specific mRNAs, to selectively block their translation. This inhibition is important for appropriate developmental regulation in C. elegans (Wightman et al, Cell 75:855-862 (1993); Slack et al, Mol. Cell 5:659-669 (2000)).
Several miRNAs, including let-7, are evolutionarily conserved from C. elegans to man, as are several let-7 targets (Ambros, Cell 107:823-826 (2001)). This conservation implies that let-7, as well as other miRNAs, may also repress the expression of specific mRNA species in mammalian cells. This hypothesis is also suggested by the similarity between miRNAs and small interfering RNAs (siRNAs), ˜21 nt double-stranded RNAs that can induce the degradation of mRNA molecules containing perfectly matched complementary targets, a process termed RNA interference (RNAi) (reviewed by Sharp, Genes Dev. 15:485-490 (2001), see also Hutv<gner et al, Curr. Opin, Genet. Dev. 12:225-232 (2002) and Zamore et al, Science 296:1265-1269 (2002), further see U.S. Pat. No. 6,506,559). However, while miRNAs are encoded within the host genome, siRNAs are generally excised from larger dsRNA precursors produced during viral infection or introduced artificially.
Because the introduction of artificial siRNAs into animal cells can induce the degradation of homologous mRNA molecules, RNAi has emerged as a useful experimental tool (Elbashir et al, Nature 411:494-498 (2001); Fire et al, Nature 391:806-811 (1998); Hammond et al, Nature 404:293-295 (2000)). However, in mammalian cells, induction of RNAi required the transfection of RNA oligonucleotides, which can be inefficient and gives rise to only a transient inhibition in target gene expression.
The present invention provides RNA molecules (miRNAs) functionally equivalent to siRNAs that can be transcribed endogenously in animal and plant cells. The invention makes possible the production of miRNAs specifically designed to inhibit the expression of mRNA containing a complementary target sequence. The miRNA molecules of the invention can be used experimentally or therapeutically to inhibit gene function.


An apparatus, system and method for emulsifying oil and water, such as for emulsifying a sizing agent for use in treating paper or paperboard, introduces a continuous phase under pressure through a continuous phase nozzle of a venturi apparatus and into a mixing section. A dispersed phase is introduced optionally under pressure into the mixing section of the venturi apparatus. The emulsion formed in the mixing section is directed through a mixed phase nozzle and out of the venturi apparatus. The mixed phase nozzle diameter of the venturi apparatus is larger than the continuous phase nozzle diameter at a ratio of greater than 1:1 and less than 4:1.

Additives used in the paper industry to impart resistance to aqueous penetrants are commonly referred to as sizing agents. The two most common synthetic sizing agents are alkyl ketene dimer (AKD) and alkenyl succinic anhydride (ASA).
AKD and ASA are hydrophobic, water-insoluble materials. These materials can be added to the pulp slurry before the sheet is formed, known as internal sizing, or can be applied to the surface of the formed web, known as surface sizing. For either application, the sizing agent should be well distributed in the aqueous system to be effective. For this reason, these water insoluble additives are commonly added in the form of aqueous, oil-in-water, emulsions.
The aqueous emulsions of sizing agents can be supplied to the paper mill in that form, or can be prepared on site. In fact, it is advantageous for some of the synthetic, cellulose reactive sizing agents to be emulsified on site. ASA, for example, is emulsified on site due to the instability of the anhydride functionality after emulsification with water.
At present, two classes of in-mill emulsification technology are used in the industry: (1) high shear, and (2) low shear. High shear emulsification entails passing ASA (or other sizing agent) and a protective colloid, starch or synthetic polymer, through a high shear turbine pump or homogenizer, with or without added surfactants. The limitations of this approach are the need for "relatively complex, expensive and heavy equipment capable of exerting high homogenizing shear and/or pressures, together with rigid procedures regarding emulsifying proportions, temperatures, etc., for producing a satisfactory stable emulsion of the particular size." (U.S. Pat. No. 4,040,900).
To address the limitations of high shear emulsification, low shear emulsification approaches have been proposed, starting with Mazzarella (U.S. Pat. No. 4,040,900) in 1977 who disclosed mixtures of ASA with 3-20 parts by weight of a surface active additive (surfactant) that were "easily emulsifiable with water in the absence of high shearing forces and under normal pressure by merely stirring, passing through a mixing valve or common aspirator." Unfortunately, such low shear emulsification can result in foam problems and poor sizing efficiency because the increased surfactant level causes surfactant to build up in the system. (C. E. Farley and R. B. Wasser, "Sizing with Alkenyl Succinic Anhydride", Chapter 3 in The Sizing of Paper, 2nd Edition, W. F. Reynolds, Ed., Tappi Press, 1989, pp 51-62).
More recently Pawlowska, et al. (WO2006/096216), disclose "an improved method of sizing paper at the wet end that will use simpler and less expensive, low shear equipment for the ASA emulsification." Pawlowska, et al. disclose a method for sizing comprising "forming, in the absence of high shearing forces, an aqueous sizing emulsion comprising an alkenyl succinic anhydride component" which is post-diluted with a cationic component. The primary difference between Pawlowska and Mazzarella is the post-dilution of the emulsion with a cationic component to enhance retention. The examples consistently demonstrate that the low shear ASA emulsions post-diluted with cationic starch are less effective sizing agents than high shear ASA emulsions, but it is argued that the simplicity of the emulsification process of the low shear ASA emulsions gives the paper maker "operational and cost benefits".
Other patents disclose use of modified starches (e.g., U.S. Pat. No. 6,210,475) or polymers (e.g., U.S. Pat. No. 6,444,024 B1), to enhance the performance of the low shear emulsification systems, but none solve the basic performance and runnability issues characteristic of the low shear system.
The definitions of "low shear" conditions versus "high shear" conditions in the literature on ASA emulsification tend to be qualitative. Typically, a list of equipment that does or does not fit the descriptor is used. "High shear" systems are: "present in Waring blenders, turbine pumps, or other extremely high speed agitators, etc.", and "are found in piston or other types of homogenization equipment" (Mazzarella). "Low shear" systems are: "merely stirring, passing through a mixing valve or common aspirator or by the usual agitation present in a stock preparation system" (Mazzarella) or, the shearing conditions "created by a device selected from the group of centrifugal pumps, static in-line mixers, peristaltic pumps, and combinations thereof" (Pawlowska). But these definitions get confused in lists of commercial emulsification equipment that include industrial low and high pressure units such as "Cytec low pressure turbine emulsifiers supplied by Cytec Industries, Inc., Nalco high pressure emulsifier systems, and National Starch turbine and venturi emulsifiers" suggesting that there are turbine pumps that fit within the low shear category. Additionally, Waring blenders are used to produce both low and high energy ASA emulsions (Chen and Woodward, Tappi J. August, 1986, pg 95) by varying the electrical voltage. So "low shear" and "high shear" systems cannot be defined simply by equipment type.
In "Principles of ASA Sizing" (CE Farley, 1987 Tappi Sizing Short Course, pg 89) there is a more quantitative definition of "high shear" and "low shear" emulsification systems: "High shear emulsification is done with a close tolerance turbine pump. The work done by the pump is such that the pressure differential between the pump outlet and inlet is about 120 to 140 psi (8.3 to 9.7 bar). ASA and starch are mixed at or near the inlet of the turbine pump." "In low shear emulsification, ASA, starch and a surfactant are mixed and passed through a series of venturis. Typical ratio of starch:ASA:surfactant is about 2.5:1:0.05. A potential disadvantage of this method is the higher level of surfactant used, which may cause "desizing" and poor ASA efficiency and foam problems." So, the distinction that Farley makes between high and low shear is that high shear systems have a pressure differential of about 120 to 140 psi (8.3 to 9.7 bar).
Similarly, Denowski et al. (US2008/0277084 A1) define low shear to be the ability to pump a liquid through a pump with a back pressure of 50 psi (3.4 bar) or less, whereas high shear is defined to require a back pressure of 150 to 300 psi (10.3 to 20.7 bar) to pump a liquid.
The need still exists in the marketplace for simpler, less expensive equipment for ASA emulsification that does not suffer from paper machine runnability issues (foam, deposits) and/or poor sizing efficiency due to high surfactant loading or poor emulsion quality.

Apparatus, system and method for emulsifying oil and water


To provide an external agent for thee skin that not only exhibits excellent effects of prevention and amelioration of skin pigmentation but also has no fear of giving adverse influences to the skin and can be used safely, there is added to an external agent for the skin one or more compound(s) selected from compounds represented by formula (I) below:

The present invention relates to an external agent for the skin and a novel compound that is applicable thereto. More particularly, the present invention relates to an external agent for the skin that contains a compound having an inhibitory activity against melanine synthesis, that is excellent in the prevention and amelioration of skin pigmentation and that is suitable for cosmetics for whitening, and a novel compound having an inhibitory activity against melanine synthesis used preferably thereto.
Skin pigmentation that causes blotches, freckles, and blackening of the skin after sunburnt is attributed to considerable sthenia of melanine synthesis, which is in turn due to activation of melanocytes in the skin. This is one of problems concerning the skin of middle- to high-aged persons. Accordingly, in order to prevent or ameliorate such a trouble on the skin pigmentation, there have been known external agents far the skin that contain ascorbic acids, aqueous hydrogen peroxide, glutathione, colloidal sulfur, hydroquinone, cathecol or the like.
However, for the prevention and amelioration of skin pigmentation as described above, ascorbic acids tend to be oxidized and thus are unstable and causes discoloration in systems that contain much moisture, such as water-contained cosmetics. Also, aqueous hydrogen peroxide has the problems of stability during storage and safety while glutathione and colloidal sulfur give strong undesirable odors so that their use in products is restricted. Further, those additives such as hydroquinone and cathecol may have the problems of safety, such as skin irritation and allergy. Therefore, there has been currently obtained no external agent for the skin which is satisfactory in the prevention and amelioration of skin pigmentation. That is, there has been a need for a novel external agent for the skin that is safe and has an excellent whitening activity.
On the other hand, among compounds represented by formula (1) used for the external agent for the skin of the present invention, those in which R is a hydrogen atom are known compounds which are described in U. S. Pat. Nos. 2,418,458/1947 and 2,418,459/1947, and the like. Further, it is also known that inulavosin among these compounds has fish toxin activity and antibacterial activity, for example, that for Staphylococcus aureus, Pseudomonas aeruginosa, and the like (Heterocycles, Vol. 41, No. 9, 1923-1926 (1995)). However, it has not been known that the compounds represented by formula (I) inclusive of the above compounds have an inhibitory activity against melanine synthesis in skin. Further, it has not been reported that the compounds represented by formula (I) are used for an external agent for the skin to prevent and ameliorate of skin pigmentation.
Under the circumstances, the present invention has been made and an object of the present invention is to provide an external agent for the skin that not only exhibits excellent effects of prevention and amelioration of skin pigmentation but also has no fear of giving adverse influences to the skin and can be used safely.
The term xe2x80x9cexternal agent for the skinxe2x80x9d as used herein refers to a composition of any type of formula that can be administered to the skin and be pooled there continuously, used in a broad concept including cosmetics, quasi-drugs, external medicines for the skin and the like.
As a result of intensive investigation with a view to achieve the above-described object, the present inventors have discovered that compounds represented by formula (I), below have strong inhibitory activity against the melanine synthesis by live melanocytes and further that they exhibit excellent effects of prevention and amelioration of skin pigmentation when they are contained in a basic formulation of external agents for the skin. Also, the present inventors have newly produced the compounds having the above-described activity. Based on these, the present invention has been completed.
That is, the present invention relates to an external agent for the skin comprising one or more compound(s) selected from compounds represented by formula (I) below:
(wherein R1, R2, R3, R4, and R5, independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and R represents a hydrogen atom, an acyl group, or a sugar residue).
In a preferred embodiment of the external agent for the skin of the present invention, content of one or more compound(s) selected from the compounds represented by formula (I) ranges in an amount from 0.0045 to 10% by weight based on the total weight of the external agent. The external agent for the skin of the present invention is used advantageously as an external agent for the skin for whitening the skin.
Also, the present invention relates to a compound represented by formula (III) below:
(wherein R1, R2, R3, R4, and R5, independently represent a hydrogen atom or an alkyl group having to 4 carbon atoms; and R7, represents an acyl group or a sugar residue).
Hereafter, the present invention will be described in detail.
(1) Compound represented by formula (I) that is an essential component of the external agent for the skin of the present invention
The external agent for the skin of the present invention contains one or more compounds represented by formula (I) above as an essential component. In formula (I), R1, R2, R3, R4, and R5, independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be either of a straight or branched chain and specifically includes a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, or a tert-butyl group, and the like. Among these, a methyl group is particularly preferred.
In formula (I), R represents a hydrogen atom of a hydroxyl group or a substituent of the hydrogen atom of a hydroxyl group, more specifically an acyl group or a sugar residue. Specifically, the acyl group includes an acyl group represented by R6xe2x80x94COxe2x80x94, wherein R6 represents an alkyl group having 1 to 17 carbon atoms or an alkenyl group having one or two double bonds and 3 to 17 carbon atoms, and mare specifically an acetyl group, a pentanoyl group, an isooctanoyl group, a stearoyl group, an isostearoyl group, an oleoyl group, an octadecadienoyl and the like. The above-described sugar residue is not limited particularly and includes any sugar residue having a glucoside linkage terminal, wherein the sugar is a monosaccharide or disachharide that can be connected through a glucoside linkage. Specific examples thereof include a glucose residue, a xylose residue, a fructose residue, an arabinose residue, a rhamnose residue, a galactose residue, a sucrose residue, a maltose residue, and the like.
Further, among the compounds represented by formula (I) above, those compounds preferably used for external agent for the skin of the present invention include compounds represented by formula (II) below:
(wherein R represents a hydrogen atom, an acyl group represented by R6xe2x80x94COxe2x80x94 or a sugar residue; in which R6 represents an alkyl group having 1 to 17 carbon atoms or an alkenyl group having one or two double bonds and 3 to 17 carbon atoms).
The compounds represented by formula (II) above are compounds represented by formula (I) in which R1, R2, R3, R4, and R5 are each a methyl group. Further, as the acyl group or sugar residue represented by R in formula (II), there may be cited the same acyl group or sugar residue in the compounds represented by formula (I) above.
Among the compounds represented by formula (I) above, those in which R is a hydrogen atom are known compounds. Methods for their synthesis are described in U. S. Pat. Nos. 2,418,458/1947 and 2,418,459/1947. The above-described compounds produced by such methods can be used in the present invention.
Further, among the compounds represented by formula (II) that are used advantageously in the present invention, the compound in which R is a hydrogen atom is known as inulavosin. It is also known that the compound has fish toxin activity and antibacterial activity, for example that for Staphylococcus aureus, Pseudomonas aeruqinosa, and the like (Heterocycles, Vol. 41, No. 9, 1923-1926 (1995)). Also, inulavosin can be produced by the method as described above.
However, it has not been known that the compounds represented by formula (I) above in which R is a hydrogen atom, inclusive of inulavosin, have an inhibitory activity against melanine synthesis in skin. Further, it has not been known that direct application of the compounds to the skin based on the above-described activity gives rise to so-called whitening effects such as excellent prevention and amelioration of skin pigmentation that would lead to blotches, freckles, blackening of skin after sunburnt or chromatosis such as melanosis. It is believed that the present inventors have found this for the first time.
Further, among the compounds represented by formula-(I), the compounds represented by formula (III) below are novel compounds that are not described in the literature. The compounds represented by formula (III) correspond to the acylated compounds or glycosides of the compounds represented by formula (I) above in which R is a hydrogen atom.
(wherein R1, R2, R3, R4, and R5, independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and R7 represents an acyl group or a sugar residue).
In formula (III) above, examples of R1, R2, R3, R4, and R5, may be cited the same as those for R1, R2, R3, R4, and R5, in formula (I) above. Further, as the aryl group or sugar residue represented by R7, there may be cited the same acyl group or sugar residue in the compounds represented by formula (I) above.
Further, among the novel compounds represented by formula (III) above, those compounds represented by formula (IV) below are compounds that can be used advantageously in the external agent for the skin of the present invention. The compounds represented by formula (IV) correspond to the acylated compounds or glycosides of the above inulavosin.
(wherein R7, represents an acyl group represented by R8xe2x80x94COxe2x80x94 or a sugar residue; in which R8 represents an alkyl group having 1 to 17 carbon atoms or an alkenyl group having one or two double bonds and 3 to 17 carbon atoms).
The compounds represented by formula (IV) above are compounds represented by formula (III) in which R1, R2, R3, R4, and R5, are each a methyl group. Further, as the acyl group or sugar residue represented by R7 in formula (IV), there may be cited the same acyl group or sugar residue in the compounds represented by formula (III) above.
Further, of these novel compounds, particularly preferred compounds to be applied to the external agent for the skin of the present invention include acetylinulavosin and glycosides of inulavosin.
These novel compounds can be produced by a conventional method using a known compound represented by formula (I) in which R is a hydrogen atom such as inulavosin, for example, by condensation reaction with an acylating agent such as aryl chloride when the targeted compound is an acylated compound, or with a halide of a sugar using silver nitrate or silver oxide as a catalyst when the targeted compound is a glycoside.
(2) External agent for the skin of the present invention
The external agent for the skin of the present invention is characterized by containing one or more compound(s) selected from the compounds represented by formula (I) above. Among the compounds represented by formula (I), preferred for the external agent for the skin of the present invention are inulavosin, acylinuolavosin, and inulavosin glycosides represented by formula (II) above. Of these, inulavosin, acetylinulavosin and inulavosin glucosides are particularly preferred.
In the present invention, addition of one or more compound(s) represented by formula (I) in a basic formulation of external agent for the skin allows exhibition of excellent whitening effect based on the inhibitory activity against melanine synthesis. The content of the above-described compound or compounds ranges preferably in an amount from 0.0005 to 10% by weight based on the total weight of the external agent for the skin. Of course, as stated above, the external agent for the skin of the present invention may include the compounds represented by formula (I) singly or in combination of two or more of them. When two or more of compounds are used in combination, a preferred range of the above-described content may be considered a range of the sum of the contents of the compounds represented by formula (I).
That is, when the external agent for the skin is used for preventing skin pigmentation that would cause blotches, freckles, blackening of skin after sunburnt or chromatosis such as melanosis, its content is desirably 0.0005% or more by weight in point of effect. Further, when the external agent far the skin is used for ameliorating skin pigmentation, its content is preferably 0.1% or more by weight, and more preferably 1% or more by weight in point of effect. As will be apparent from the experimental results described hereinbelow, when the content of the above-described compound is less than 0.0005% by weight, the tendency is observed that the inhibitory activity against melanine synthesis is decreased considerably while in spite of use of the amount of above 10% by weight, the effect reaches a plateau. Therefore, it is desirable that the external agent for the skin of the present invention contains the compound(s) in the above-described range.
Also, the external agent for the skin of the present invention is desirably one that is used in the form in which it is pooled on the skin continuously in view of the characteristics of the compound or compounds activity represented by general formula (I) that the external agent for the skin of the present invention contains as an essential component. In this respect, it can be said that most external agents for the skin conventionally used take application forms desirable for the external agent for the skin of the present invention. Although a washing agent is one embodiment of the external agent for the skin of the present invention, it cannot be said to be a preferred embodiment of the external agent for the skin of the present invention since its application form is temporary in nature, on the other hand, a pack material or the like has a shielding effect, though its contact time with skin is short, so that it is a preferred embodiment of the external agent for the skin of the present invention.
The external agent for the skin of the present invention can be obtained by blending one or more compounds selected from the compounds represented by formula (I) above in a basic formulation far external agents for the skin conventionally used for external agents for the skin, such as external medicines for the skin, cosmetics, and the like by a conventional method and can be produced in the same manner as the conventional external agents for the skin except that one or more compounds selected from the compounds represented by formula (I) above is or are blended therein.
As components of the basic formulation for the above-described external agents for the skin, there can be cited, for example, a moisture component, an oil component, a power component, a surfactant, a tackifier, a colorant, a fragrant, an anti-oxidant, a pH adjusting agent, a chelating agent, a preservative and the like. In addition to the compounds represented by formula (I), the external agent for the skin of the present invention may optionally contain one or more medical components such as a humectant, an ultraviolet shielding agent, and an anti-inflammatory agent. Further, in addition to the compounds represented by formula (I), the external agent for the skin of the present invention may optionally contain one or more whitening components such as a whitening agent, for example, pantetheine-S-sulfonic acid, isoferulic acid, magnesium phosphate ascorbic acid salt, arbutin, kojic acid, rinolic acid, methyl tinplate, and the like.
Further, the application form of the external agent for the skin of the present invention may be of any type conventionally used for this type of external agent for the skin and includes, for example, ointment, cream, emulsion, lotion, pack and the like application forms.
Applications of the external agent for the skin of the present invention include cosmetics, quasi-drugs, external medicine for the skin and the like. Further, the external agents for the skin can be used advantageously for whitening.

Benzo[b]pyran derivatives useful as external agents for the skin


Embodiments of the invention provide a magnetic read/write device capable of reading/writing data even when a reversal of the output polarity of the readback signal occurs. In one embodiment, a magnetic read/write device is provided which constantly checks the output polarity based on the polarity of the waveform of a signal obtained as a result of equalizing the waveform of a readback signal of gray code (indicating a cylinder number) in each servo sector by use of a matched filter (MF), or based on the waveform of a readback signal read from areas of a magnetic disk which store a special pattern for detecting the output polarity. When a polarity reversal has occurred, the magnetic read/write device assumes that a read error has occurred and performs processing so as not to perform any track seek or track following operation using decoded positional information. The magnetic read/write device then reverses the polarity of the output signal by use of a polarity reversing unit provided within or on the input side of a read/write channel, and resumes servo and read/write operations.

The present invention relates to a magnetic read/write device which writes data to a recording medium as magnetic information by use of a write head and then reads and decodes the written magnetic information by use of a read head. More particularly, the present invention relates to a technique of preventing malfunction due to a reversal in the polarity of the read output from the read head.
One method for increasing the recording density of a magnetic read/write device is to use a GMR (Giant Magnetoresistive) head, which has become very common. A GMR head includes a free layer whose magnetization direction can be changed by an external magnetic field. Since the resistance of the GMR element changes with the magnetization direction of the free layer, written information (on the disk) can be read by converting this change in the resistance into voltages.
Even though the polarity of this (voltage) output usually does not change, a polarity reversal may possibly occur while the head is operating, depending on the configuration of the head. If this happens, the waveform of the read signal will become inverted. Conventional GMR heads are designed such that no output polarity reversal occurs. However, as the device size and the distance between the read shields have been reduced, it has become difficult to ensure sufficient resistance to polarity reversal. To provide a reduced head device size, the "automatic pinning type" GMR head has been studied and developed in which an antiferromagnetic layer is not disposed adjacent the pinned layer. The "automatic pinning type" GMR head has very good read performance but is disadvantageous in that the magnetization direction of the pinned layer tends to be readily reversed due to contact with the medium, etc.
If a reversal in the polarity of the read output has occurred, the magnetic read/write device may become unable to decode read positional information, or may incorrectly decode it, which prevents the magnetic read/write device from positioning the head. Under the worst case conditions, the magnetic read/write device might run out of control and break down. Even if such a runaway does not occur, the magnetic read/write device will become unable to position the head, leading to an inability to decode user data.
To accommodate reversal of the output polarity due to degradation of the read head, Patent Document 1 (Japanese Patent Laid-Open No. 2000-251203) discloses a method which includes the steps of: when a read data error has occurred, reading a reference signal (or an address mark) from the servo data and determining the polarity of the output; and upon detecting a polarity reversal, supplying a refresh current to the read head to return the output polarity to normal.
In the case of the "pre-servo write" system, to accommodate reversal of the output polarity due to the difference between each head in the magnetic read/write device and each head (in the servo writer) used to perform servo write operation to the device, Patent Document 2 (Japanese Patent Laid-Open No. 2003-85704) discloses a method which stores the output polarity of each head and thereby allows the magnetic read/write device to read servo information even when there is a polarity difference between these heads by utilizing the polarity switching function of the read channel.

Magnetic read/write device preventing malfunction due to reversal in polarity

Hitachi Global Storage Technologies, Netherlands, B.V.


Single layer anti-reflective hard-coat and methods of making same are disclosed and in particular comprise a structured surface, preferably a nano-structured surface. The hard-coat preferably a hardness above 0.5 GPa, more preferably above 0.7 GPa and most preferably above 1.0 GPa as measured by nano-indentation and/or a reduced tensile modulus above 3 GPa, more preferably above 8.5 GPa or 20 GPa, most preferably above 40 GPa as measured by nano-indentation and/or a scratch resistance above 5 mJ μm-3, preferably above 15 or 30 mJ μm-3, preferably above 60 mJ μm-3 as measured by nano-indentation, and/or contains an amount of inorganic nano-particles from 5 to 75 weight %, preferably from 15 to 50 weight % relative to the weight of the second material present in the hard-coat. Preferably, the spatial length scale of the refractive index gradient in the single layer hard-coat is between 10 and 1000 nm; in particular between 100 and 200 nm.

The invention relates to a mechanically durable, single coating with anti-reflective properties, process for manufacturing such a coating and to compositions for the manufacturing of such a coating. The coatings typically exhibit a nano-structured surface.
Mechanically durable coatings, also known as hard-coats, are well known for their hardness, modulus, scratch resistance and optical transparency. Generally, a combination of these properties is achieved by combining chemically crosslinked materials with inorganic fillers whose dimensions are in the nanometer range, thus resulting in filled materials transparent to light in the visible wavelengths range. [Atushi et al (Conference proceedings, RadTech, Asia, 1997)]
Whilst these coatings are optically transparent, they are also smooth and as is the case for all smooth coatings this results in a certain degree of reflection of light from the coating/air interface (D. Chen, Solar Energy Materials & Solar Cells, 86 (2001) 313-336). This property has been recognized in the art as a problem in many different applications (D. Chen, Solar Energy Materials & Solar Cells, 86 (2001) 313-336) and has been addressed by tailoring of the thickness of the applied coating and its respective refractive index. This may lead to improved anti-reflective performance, as measured by an increase in transmission of light with respect to the substrate. It has been shown that it is possible to achieve an increase in transmission over the whole visible region of the light spectrum by preparing multilayer systems of coatings in which each coating has a carefully selected thickness and refractive index (U.S. Pat. No. 5,582,859).
However, multilayer coatings suffer from two sets of problems. The first is that the anti-reflective performance of multilayer coatings suffers from angle-dependency (D. Chen, Solar Energy Materials & Solar Cells, 86 (2001) 313-336). This means that transmission will vary from the normal to oblique angles. Secondly, reproducible processing of such multilayer coatings with precisely controlled thickness and optical properties is difficult and therefore costly and time-consuming.
Alternatively, a single coating can be made anti-reflective by having a controlled surface structure. (Steiner et al., Science, Vol 283, pg 520-522, 1999, Ibn-Elhaj and Schadt, Nature, Vol 410, pg 796-799, 2001). Such single anti-reflective coatings based on controlled surface structure exhibit less angle-dependency of their optical properties but do not possess the attractive mechanical robustness of hard-coats. This is especially relevant for films used in anti-reflective applications, as these are often very thin.
Therefore, it would be desirable to have a coating system with the mechanical robustness of a hard-coat that may be applied as a single layer while still having sufficient anti-reflective properties.
Thus, the object of the present invention is to provide a coating comprising an anti-reflective surface that has the durable mechanical properties of hard coats (hardness, modulus, scratch resistance) but which achieve anti-reflective properties in a single coating.
It has now been found that single layer anti-reflective hard-coats may be manufactured by a process comprising the steps of:
a) applying a mixture on a substrate, which mixture comprises
                i) at least a first material which does not crosslink under the conditions chosen in step b)        ii) at least a second material which does crosslink under the conditions chosen in step b)        iii) nano-particles, and        iv) optionally at least one solvent,b) inducing crosslinking in the mixture applied to the substrate,c) subsequently removing at least part of the first material.
Advantageously, the mixture in step a) is a homogenous mixture. In the framework of the invention, a mixture is homogenous when the mixture does not scatter visible light after application to the substrate and prior to crosslinking, the scattering being observed as cloudiness in the film by the naked eye and/or a loss of transmission of light in the visible region of the electromagnetic spectrum. Furthermore, phase separation prior to crosslinking may also be observed by optical, optionally polarizing, microscopy, as is often done to determine the miscibility of polymer blends.
In the framework of the invention the term "(nano) structured surface" refers to a surface which exhibits ridges and troughs that may be randomly distributed, see FIG. 6. More specifically the height of the ridges (h) and the average distance (λC) between the ridges should be in the micrometer to nanometer range. In a preferred embodiment suitable for anti-reflective applications the height of the ridges (h) should be in the range of 50-200 nm and the lateral distance between ridges (λC) should be shorter than the shortest wavelengths of visible light (λlight), such as less than 400 nm.
Anti-reflective films or coatings are herein defined as films or coatings that (when deposited onto glass as a substrate) have a transmission higher than the transmission of the substrate in at least part of the visible light spectrum. Typically, such films are free or substantially free of structural features large enough to be capable of scattering visible light, and such films should thus be optically transparent.
Single layer anti-reflective hard-coats may advantageously be applied to any optical systems were the anti-reflective coating is likely to be in contact with some sort of mechanical force, for example where cleaning of the surface may periodically be required. The hard-coats according to the invention could therefore advantageously be applied to any display application in general.
The single layer anti-reflective hard-coats according to the invention show less angle dependence of the anti-reflective performance in comparison to multi-layer systems.
Therefore, the combination of durable mechanical properties as well as improved anti-reflective performance at oblique angles will allow for the use of these single layer anti-reflective hard-coats in applications were mechanical durability and anti-reflective performance at oblique angles or on non-flat substrates are advantageous. These applications include anti-reflective hard coatings for automobile and airplane wind screens, television tubes, flexible displays and spectacles.
In the process according to the invention a first material is used which does not crosslink under the conditions chosen in the subsequent crosslinking step. Thus, in principle, a wide variety of materials are suitable to be used as the first material. However, the combination of the first material and all other materials should advantageously result in a homogenous mixture, which is still homogenous prior to crosslinking. After the induction of crosslinking the mixture phase separates into domains which may advantageously have a size in the order of magnitude of nanometers. Depending on the desired properties of the single layer anti-reflective coating, the size of the domains may be anywhere up to hundreds of nanometers, however smaller domains are preferred.
In order for a material to be suitable as the first material it must be compatible (soluble) in the components comprising the second material. In the framework of the invention a compatible material refers to one which does not lead to phase separation prior to cross-linking, i.e. leads to homogeneous coatings prior to cross-linking. This can be realised by the second material being similar in terms of polarity and chemical structure to the components comprising the second materials but lacking the chemical reactivity toward the chosen crosslinking mechanism. The first material may also undergo specific interaction (e.g. hydrogen bonding) with the components of the second materials, which could lead to compatible (homogeneous) coatings prior to cross-linking.
It has been found that lyotropic liquid crystalline materials are suitable for use as a first material. In a preferred embodiment hydroxypropyl cellulose, being a lyotropic liquid crystalline polymer, is used. Surprisingly hydroxypropyl cellulose is considerably higher in polarity than the components comprising the second material yet show no evidence of macro or micro-phase separation prior to cure. Many materials are in principle suitable as the first material as long as good compatibility exists between the first and second material prior to crosslinking. Suitable therefore are also thermotropic liquid crystalline polymers, non-polymeric liquid crystalline materials and the first material may also be selected from the group consisting of polymeric, non-polymeric and isotropic materials.
In a preferred embodiment the first material is a water-soluble material. Use of a water-soluble first material has the advantage that it allows for the removal of at least part of the first material in an environmentally friendly way, i.e. washing with water.
In the process according to the invention a second material is used which does crosslink under the conditions chosen in the subsequent cross-linking step. In principle, a wide variety of materials is suitable to be used as the second material. However, the combination of the second material and all other materials present in the mixture should advantageously result in a homogenous mixture, which is still homogenous prior to crosslinking.
As mentioned, in principle a wide variety of materials is suitable to be used as the second material, for example monomers or oligomers having crosslinking groups. Monomers or oligomers having only one crosslinking group per molecule may be used, but only in combination with other crosslinking components that do have at least two crosslinking groups. Preferably monomers or oligomers having at least two or more crosslinking groups per molecule are used. It is also possible that the second material comprises a mixture of compounds that after the induction of crosslinking in step b, together form a crosslinked phase. The mixture may comprise compounds that are by itself crosslinking, such as for example different acrylates or it may comprise compounds that will not crosslink by itself but which form a crosslinked phase in combination with another compound after initiation of the crosslinking reaction.
Examples of monomers suitable for use as a second material and having at least two crosslinking groups per molecule include monomers containing (meth)acryloyl groups such as trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polybutanediol di(meth)acrylate, tripropyleneglycol di(meth)acrylate, glycerol tri(meth)acrylate, phosphoric acid mono- and di(meth)acrylates, C7-C20 alkyl di(meth)acrylates, trimethylolpropanetrioxyethyl (meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy pentacrylate, dipentaerythritol hexacrylate, tricyclodecane diyl dimethyl di(meth)acrylate and alkoxylated versions, preferably ethoxylated and/or propoxylated, of any of the preceding monomers, and also di(meth)acrylate of a diol which is an ethylene oxide or propylene oxide adduct to bisphenol A, di(meth)acrylate of a diol which is an ethylene oxide or propylene oxide adduct to hydrogenated bisphenol A, epoxy(meth)acrylate which is a (meth)acrylate adduct to bisphenol A of diglycidyl ether, diacrylate of polyoxyalkylated bisphenol A, and triethylene glycol divinyl ether, adduct of hydroxyethyl acrylate, isophorone diisocyanate and hydroxyethyl acrylate (HIH), adduct of hydroxyethyl acrylate, toluene diisocyanate and hydroxyethyl acrylate (HTH), and amide ester acrylate.
Examples of suitable monomers having only one crosslinking group per molecule include monomers containing a vinyl group, such as N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl imidazole, vinyl pyridine; isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloyl morpholine, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, caprolactone acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, beta-carboxyethyl (meth)acrylate, phthalic acid (meth)acrylate, isobutoxymethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, t-octyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, butylcarbamylethyl (meth)acrylate, n-isopropyl (meth)acrylamide fluorinated (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, N,N-diethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether; and compounds represented by the following formula (1)CH2═C(R6)—COO(R7O)m—R8  (1)wherein R6 is a hydrogen atom or a methyl group; R7 is an alkylene group containing 2 to 8, preferably 2 to 5 carbon atoms; and m is an integer from 0 to 12, and preferably from 1 to 8; R8 is a hydrogen atom or an alkyl group containing 1 to 12, preferably 1 to 9, carbon atoms; or, R8 is a tetrahydrofuran group-comprising alkyl group with 4-20 carbon atoms, optionally substituted with alkyl groups with 1-2 carbon atoms; or R8 is a dioxane group-comprising alkyl group with 4-20 carbon atoms, optionally substituted with methyl groups; or R8 is an aromatic group, optionally substituted with C1-C12 alkyl group, preferably a C8-C9 alkyl group, and alkoxylated aliphatic monofunctional monomers, such as ethoxylated isodecyl (meth)acrylate, ethoxylated lauryl (meth)acrylate, and the like.
Oligomers suitable for use as the second material are for example aromatic or aliphatic urethane acrylates or oligomers based on phenolic resins (ex. bisphenol epoxy diacrylates), and any of the above oligomers chain extended with ethoxylates. Urethane oligomers may for example be based on a polyol backbone, for example polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, acrylic polyols, and the like. These polyols may be used either individually or in combinations of two or more. There are no specific limitations to the manner of polymerization of the structural units in these polyols. Any of random polymerization, block polymerization, or graft polymerization is acceptable. Examples of suitable polyols, polyisocyanates and hydroxylgroup-containing (meth)acrylates for the formation of urethane oligomers are disclosed in WO 00/18696, which is incorporated herein by reference.
Combinations of compounds that together may result in the formation of a crosslinked phase and thus that in combination are suitable to be used as the second material are for example carboxylic acids and/or carboxylic anhydrides combined with epoxies, acids combined with hydroxy compounds, especially 2-hydroxyalkylamides, amines combined with isocyanates, for example blocked isocyanate, uretdion or carbodiimide, epoxies combined with amines or with dicyandiamides, hydrazinamides combined with isocyanates, hydroxy compounds combined with isocyanates, for example blocked isocyanate, uretdion or carbodiimide, hydroxy compounds combined with anhydrides, hydroxy compounds combined with (etherified) methylolamide ("amino-resins"), thiols combined with isocyanates, thiols combined with acrylates (optionally radical initiated), acetoacetate combined with acrylates, and when cationic crosslinking is used epoxy compounds with epoxy or hydroxy compounds.
Further possible compounds that may be used as the second material are moisture curable isocyanates, moisture curable mixtures of alkoxy/acyloxy-silanes, alkoxy titanates, alkoxy zirconates, or urea-, urea/melamine-, melamine-formaldehyde or phenol-formaldehyde (resol, novolac types), or radical curable (peroxide- or photo-initiated) ethylenically unsaturated mono- and polyfunctional monomers and polymers, e.g. acrylates, methacrylates, maleate/vinyl ether), or radical curable (peroxide- or photo-initiated) unsaturated e.g. maleic or fumaric, polyesters in styrene and/or in methacrylates.
In a specific embodiment, it is possible that the second material comprises nano-particles present in the mixture as described in step a) of the process according to the invention. In that case, at least a significant part of the nano-particles must have crosslinking groups on their surface, in a preferred embodiment all nano-particles have crosslinking groups on their surface.
The amount of the first material, i.e. the relative amount of all compounds that do not crosslink in step b, but excluding any solvent that may be present in step a), and the amount of the second material, i.e. the relative amount of all compounds that after crosslinking will be part of the crosslinked phase may vary within wide ranges. Preferably, the mixture comprises the second material and the first material in a ratio of between 1:4 to 4:1, more preferably, the mixture comprises the second material and the first material in a ratio of between 2:3 and 3:2.
The concentration of all non-solvent components in a mixture that does comprise at least one solvent may also vary within wide ranges, e.g. between 1 and 95 wt % relative to the total weight of the mixture including the solvent. The concentration of the non-solvent components depends for example on the process by which the mixture is applied to the substrate, the temperature, the viscosity etc.
When the mixture is applied to the substrate by spin coating, the total amount of non-solvent components is typically in the range of 1-20 wt %, relative to the total weight of the mixture.
In the framework of this invention the term "nano-particles" is defined as particles of which the majority has a diameter of less than a micrometer. For non-spherical particles the longest straight line that can be drawn from one side of a particle to the opposite side may be used as the value for the diameter. In a preferred embodiment, the majority of the nano-particles have a diameter of less than 400 nm, more preferably the majority of particles have a diameter of less than 50 nm. Most preferably all particles have a diameter smaller than 50 nm. Most preferably, particles used have such a diameter that they do not (significantly) influence the transparency of the eventual coating. Processes for determining the particle diameter include BET adsorption, optical or scanning electron microscopy, or atomic force microscopy (AFM) imaging.
In the process according to the invention the film may comprise either organic or inorganic nano-particles. Examples of organic nano-particles are carbon nanotubes or nanospheres. Preferably, the nano-particles are inorganic nano-particles. Suitable inorganic particles are for example oxide particles. Preferred oxide particles are particles of an oxide selected from the group of aluminum oxide, siliciumoxide, zirconium oxide, titanium oxide, antimony oxide, zinc oxide, tin oxide, indium oxide, and cerium oxide. It is also possible to use a mixture of particles from different oxides or to use particles of mixed oxides. Preferably, the nano-particles are particles of aluminum oxide, zirconium oxide or silica oxide. The refractive index of the coating and effective refractive index of the coating/air interface can in part be tuned by the choice of oxide used.
In principle a wide variety of nano-particles may be used. However, the combination of the nano-particles and all other materials present in the mixture in step a) of the process according to the invention, should advantageously result in a homogenous mixture, which is still homogenous prior to crosslinking.
It has been found that it is often advantageous to use stabilized nano-particles in the process according to the invention. In the framework of the invention, the term "stabilized particles" means particles that have organic groups on their surface. These organic groups may or may not comprise a polymerizable groups. Herein, nano-particles having crosslinking groups on their surface are called "reactive nano-particles". Such reactive nano-particles may or may not comprise additional, non-polymerizable organic groups. Particles wherein the organic groups on the surface do not comprise any polymerizable group are called "passive nano-particles".
In an advantageous embodiment of the invention, at least part of the nano-particles have crosslinking groups on their surface. In a further preferred embodiment, the nano-particles are metal oxide particles having crosslinking groups on their surface.
In an advantageous embodiment of the process according to the invention, the mixture in step a) consists of or comprises reactive nano-particles, passive nano-particles or a mixture thereof. When the second material in the process according to the invention consists of reactive nano-particles only, no other crosslinking component may be present. The nano-structured film or coating is formed after crosslinking of the crosslinking groups present on the surface of the reactive nano-particles and subsequent removal of at least part of the first material.
In a preferred embodiment of the process according to the invention, all nano-particles are reactive.
The preparation of reactive and passive nano-particles as such is known in the art, and has been described in e.g. U.S. Pat. No. 6,025,455.
The nano-particles used in the process according to the invention are often provided in the form of a suspension. One of the problems encountered with suspensions of (combinations of) mixtures is their stability with respect to phase separation and flocculation. It is a general belief in the art that addition of polymers to a suspension of colloidal particles results in phase separation. This mechanism is known in the literature as 'depletion flocculation' (A. Vrij, Pure & Appl. Chem. 48, 1976, p 471) For example, addition of a common polar linear polymer, i.e. poly(ethyleneglycol) or hyperbranched polyester-amides to a suspension of multi-functional acrylates with nanosilica particles results in inhomogeneous films prior to cure, despite the similarity in polarity.
Surprisingly, it has now been found that the addition of the lyotropic liquid-crystalline hydroxypropyl cellulose does not result in an opaque suspension when added to a mixture of acrylated nano-particles, dipentaerythritolpentaacrylate and ethyxylated trimethylolpropane triacrylated of time in methanol. At room temperature, this mixture is even stable for a considerable period of time.
Without wanting to be bound by theory, it is our current belief that the lyotropic nature of the hydroxypropyl cellulose together with its high hydroxyl functionality may stabilize the suspension from flocculation, thus ensuring homogenous films upon deposition and prior to crosslinking. In a preferred embodiment, hydroxypropyl cellulose is used as the first material in the process according to the invention.
A wide variety of substrates may be used as a substrate in the process according to the invention. Suitable substrates are for example flat or curved, rigid or flexible substrates including films of for example polycarbonate, polyester, polyvinyl acetate, polyvinyl pyrollidone, polyvinyl chloride, polyimide, polyethylene naphthalate, polytetrafluoro ethylene, nylon, polynorbornene or amorphous solids, for example glass or crystalline materials, such as for example silicon or gallium arsenide. Preferred substrates for use in display applications are for example glass, polynorbornene, polyethersulfone, polyethyleneterphtalate, polyimide, cellulose triacetate, polycarbonate and polyethylenenaphtalate.
A free-standing single layer anti-reflective hard-coat film or coating obtainable by a process according to the invention may be obtained by preparing a film or coating on a substrate and subsequently removing the film or coating from the substrate after crosslinking. The removal of the film or coating from the substrate should always take place after crosslinking but may take place before or after removal of the first material.
The mixture may be applied onto the substrate by any process known in the art of wet coating deposition. Examples of suitable processes are spin coating, dip coating, spray coating, flow coating, meniscus coating, capillary coating and roll coating.
In principle it is possible to apply the mixture to the substrate without the use of a solvent, for example by using nano-particles and mixing them into a liquid mixture of the other components. However, often this results in very unstable formulations and/or in an increase in viscosity that makes application of the mixture onto the substrate difficult, especially as very thin films.
Typically, the first material, the second material and the nano-particles are mixed with at least one solvent to prepare a mixture that is suitable for application to the substrate using the chosen method of application. In principle, a wide variety of solvents may be used. However, the combination of the solvents and all other materials present in the mixture should advantageously result in a homogenous mixture, which is still homogenous prior to crosslinking.
Nano-particles typically are added to the mixture in the form of a suspension. The same solvent may be used to adjust the mixture so that it has the desired properties. However, other solvents may also be used
Examples of solvent that may be suitable are 1,4-dioxane, acetone, acetonitrile, chloroform, chlorophenol, cyclohexane, cyclohexanone, cyclopentanone, dichloromethane, diethyl acetate, diethyl ketone, dimethyl carbonate, dimethylformamide, dimethylsulphoxide, ethanol, ethyl acetate, m-cresol, mono- and di-alkyl substituted glycols, N,N-dimethylacetamide, p-chlorophenol, 1,2-propanediol, 1-pentanol, 1-propanol, 2-hexanone, 2-methoxyethanol, 2-methyl-2-propanol, 2-octanone, 2-propanol, 3-pentanone, 4-methyl-2-pentanone, hexafluoroisopropanol, methanol, methyl acetate, methyl acetoacetate, methyl ethyl ketone, methyl propyl ketone, n-methylpyrrolidone-2, n-pentyl acetate, phenol, tetrafluoro-n-propanol, tetrafluoroisopropanol, tetrahydrofuran, toluene, xylene and water. Alcohols, ketones and esters based solvents may also be used, although the solubility of acrylates may become an issue with high molecular weight alcohols. Halogenated solvents (such as dichloromethane and chloroform) and hydrocarbons (such as hexanes and cyclohexanes), may also be suitable.
The same solvents may be suitable for washing at least part of the first material away. The preferred solvent for the removal of at least part of the first material is water.
Any cross-linking method that may selectively cause the second material to crosslink but that does not result in crosslinking of the first material is suitable to be used in the process according to the invention. Suitable ways to initiate crosslinking are for example electron beam radiation, electromagnetic radiation (UV, Visible and Near IR), thermally and by adding moisture, in case moisture curable compounds are used as the second material. In a preferred embodiment crosslinking is achieved by UV-radiation. The UV-crosslinking may take place through a free radical mechanism or by a cationic mechanism, or a combination thereof. In another preferred embodiment the crosslinking is achieved thermally.
An initiator may be present in the mixture to initiate the crosslinking reaction. The amount of initiator may vary between wide ranges. A suitable amount of initiator is for example between above 0 and 5 wt % with respect to total weight of the compounds that take part in the crosslinking reaction. The relative amount of initiator will determine the kinetics of the crosslinking step and can thus be used to affect the (nano) surface structure and thus the anti-reflective performance.
When UV-crosslinking is used to initiate crosslinking of the second material, the mixture preferably comprises a UV-photo-initiator. A photo-initiator is capable of initiating a crosslinking reaction upon absorption of light, thus, UV-photo-initiators absorb light in the Ultra-Violet region of the spectrum. Any known UV-photo-initiators may be used in the process according to the invention, with the proviso that the mixture preferably remains homogenous.
Any process that selectively or preferentially removes the first material in step c) while the crosslinked material is not removed or removed to a smaller extent is suitable for use in step c). An example of a process for the removal of the first material is washing with a solvent, in which the first material dissolves and the crosslinked material does not dissolve and/or does not swell. Preferably, a solvent is used in which only the first material dissolves. Other possible processes are for example evaporation of at least part of the first material or decomposition or degradation or pyrolysis or sublimation of at least part of the first material. Other techniques that may be used are mechanical stripping or brushing. In a preferred embodiment the first material is removed by washing with a solvent. In a further preferred embodiment the first material is at least partially removed with water.
The mixture used in the process according to the invention may also comprise an adhesion promoter. An adhesion promoter is a component that improves the adhesion of the nano-structured film or coating to the substrate. The adhesion promoter is preferably included in the mixture before deposition in an amount ranging from 0.1 to 5 wt % based on the total weight of compounds in the mixture and under the condition that the film is homogenous prior to crosslinking.
Suitable promoters for the adhesion of the film or coating to a glass or other substrates are for example acrylated trimethoxy silane monomers. Examples of silane adhesion promoters include: γ-mercaptopropylmethylmonomethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmonoethoxysilane, γ-mercaptopropyldiethoxysilane, γ-mercaptopropyltriethoxysilane, β-mercaptoethylmonoethoxysilane, β-mercaptoethyltriethoxysilane, β-mercaptoethyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxylpropyltrimethoxysilane, γ-glycidoxyl propylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane. Examples of commercially available products of these compounds include SILAACE S310, S311, S320, S321, S330, S510, S520, S530, S610, S620, S710, S810 (manufactured by Chisso Corp.), Silquest A-174NT (manufactured by OSI Specialties—Crompton Corp.). SH6062, AY43-062, SH6020, SZ6023, SZ6030, SH6040, SH6076, SZ6083 (manufactured by Toray-Dow Corning Silicone Co., Ltd.), KBM403, KBM503, KBM602, KBM603, KBM803, KBE903 (manufactured by Shin-Etsu Silicone Co., Ltd.), and the like. Also acidic adhesion promoters such as acrylic acid may be used. Phosphate esters such as Eb168 or Eb170 from UCB are feasible adhesion promoters.
Any other additive may be added to the films or coatings according to the invention. It remains however advantageous that the mixture is homogenous prior to cross-linking.
The composition of the mixture as well as the processes chosen for the various steps and the exact process conditions of the steps in the process according to the invention will together determine the surface structure of the film or coating obtained. The surface structure (i.e. the depth of the troughs and distance between ridges, see FIG. 6) is e.g. affected by temperature, deposition process and the chosen method of crosslinking. If UV radiation is used, the wavelength and the intensity during crosslinking, the amount of photo-initiator and the irradiation time will all influence the surface structure. Secondly the mechanical properties of the film or coating are affected by the chosen methods and conditions. For example, the crosslink density of the crosslinked phase may be increased by heating the film or coating during or after crosslinking. By increasing the crosslink density, the hardness, the modulus and Tg of the resulting film or coating may be increased. Furthermore, such an extra heating step allows the adhesion promoter to react with the substrate and thus improves adhesion and also scratch resistance.
As a result of the above described process, a single layer anti-reflective hard coat is obtained. Such coatings are herein referred to as coatings according to the invention and these coatings typically exhibit a nano-structured surface whereas conventional single layer hard-coats are smooth on the nano-scale level.
In a preferred embodiment, a hard-coat according to the invention has a hardness above 0.5 GPa as measured by nano-indentation. Hardnesses of above 0.7 or even above 1.0 are even more preferred A method of measuring the hardness by nano-indention is described in the experimental section.
In another preferred embodiment, the hard-coat according to the invention has a reduced tensile modulus above 3 GPa, as measured by nano-indentation. A reduced tensile modulus of above 8.5 such as above 20 or above 40 are even more preferred. A method of measuring the reduced tensile modulus by nano-indention is described in the experimental section.
In another preferred embodiment, the hard-coat according to the invention has a scratch resistance above 5 mJ μm−3 measured by nano-indentation. A scratch resistance of above 15 such as above 30 or even above 60 is more preferred.
It will be appreciated that it is difficult if not impossible to measure hardness, reduced tensile modulus or scratch resistance of hard-coats when they have a structured or nano-structured surface. Therefore, it will be clear to a skilled person that when it is stated herein that a hard-coat according to the invention has a hardness, reduced tensile modulus or scratch resistance of a certain value, that it is meant that the bulk of the material of the hard-coat has these properties.
A method of measuring the scratch resistance by nano-indention has been described in the experimental section.
A further preferred hard-coat combines at least two of the features described above.
In general, the hard-coats according to the invention have a refractive index value that decreases from that refractive index value of the crosslinked phase to that of air over a spatial length scale. Preferably, the length scale of the refractive index gradient is between 10 and 1000 nm, more preferably the length scale is between 100 and 200 nm. The shape of the surface, i.e. the ridges and troughs, achieves the gradient of the refractive index.
In a preferred embodiment of the films or coatings according to the invention, the majority of the ridges are smaller than 1000 nm. A useful way to characterize the surface structure is by using AFM imaging combined with radial density Fourier transformation, as described in Caro et al., Chapter 4, Volume 5 in Handbook of Surfaces and Interfaces of Materials, Ed. H. S. Nalwa, Academic Press, 2001. This analysis function is standard available on AFM instruments of Digital Instruments. Such an approach typically yields a critical length scale, characterizing the surface structure. In an optimum embodiment, this critical length scale is below the wavelength of visible light, i.e. 350 nm. Preferably, the nano-structured films or coatings according to the invention have such a structure that the critical wave vector of the radial fourier density transformation for an uncorrelated density distribution is above 2 pi/600 nm, more preferably above 2 pi/400 nm.
In a preferred embodiment, the nano-structured films or coatings according to the invention do not reduce the optical transmission characteristics of a substrate on which they are present to visible wavelengths of the electromagnetic spectrum.
In another preferred embodiment, the nano-structured films or coatings according to the invention increases the optical transmission of a substrate on which they are present to visible wavelengths of the electromagnetic spectrum.

Preparation of a mechanically durable single layer coating with anti-reflective properties


Embodiments of the present disclosure provide methods, devices, and systems for performing a programming operation on an array of non-volatile memory cells. One method includes programming a number of cells to a number of final data states. The method includes performing, prior to completion of, e.g., finishing, the programming operation, an erase state check on a subset of the number of cells, which were to be programmed to an erased state.

Memory devices are typically provided as internal, semiconductor, integrated circuits in computers or other electronic devices. There are many different types of memory including random-access memory (RAM), read only memory (ROM), dynamic random access memory (DRAM), synchronous dynamic random access memory (SDRAM), and flash memory, among others.
Flash memory devices are utilized as non-volatile memory for a wide range of electronic applications. Flash memory devices typically use a one-transistor memory cell that allows for high memory densities, high reliability, and low power consumption.
Uses for flash memory include memory for personal computers, personal digital assistants (PDAs), digital cameras, and cellular telephones. Program code and system data, such as a basic input/output system (BIOS), are typically stored in flash memory devices. This information can be used in personal computer systems, among others.
Two common types of flash memory array architectures are the "NAND" and "NOR" architectures, so called for the logical form in which the basic memory cell configuration of each is arranged. In the NOR array architecture, the floating gate memory cells of the memory array are typically arranged in a matrix.
The gates of each floating gate memory cell of the array matrix are typically coupled by rows to word lines and their drains are coupled to column bit lines. The NOR architecture floating gate memory array is accessed by a row decoder activating a row of floating gate memory cells by selecting the word line coupled to their gates. The row of selected memory cells then place their data values on the column bit lines by flowing different currents depending on if a particular cell is in a programmed state or an erased state.
A NAND array architecture also arranges its array of floating gate memory cells in a matrix such that the gates of each floating gate memory cell of the array are coupled by rows to word lines. However each memory cell is not directly coupled to a column bit line by its drain. Instead, the memory cells of the array are coupled together in series, source to drain, between a source line and a column bit line.
Memory cells in a NAND array architecture can be programmed to a desired state. For example, electric charge can be placed on or removed from the floating gate of a memory cell to put the cell into a number of data states. For example, a single level cell (SLC) can represent two binary states, e.g., 1 or 0. Flash memory cells can also store more than two binary states, e.g., 00, 01, 10, or 11. Such cells may be referred to as multi state memory cells, multibit cells, or multilevel cells (MLCs). MLCs can allow the manufacture of higher density memories without increasing the number of memory cells since each cell can represent more than one bit. MLCs can have more than one programmed state, e.g., a cell capable of representing two bits can have three programmed states and an erased state.
Reading of memory cells can be accomplished by applying an appropriate voltage to the control gate and the drain and comparing the drain to source current, which can indicate the voltage threshold (Vt) of the cell, against a reference current, e.g., a "trip point," to determine the state of the memory cell. In an example data read operation, e.g., 0 volts can be applied to a selected word line, e.g., to the control gate of a cell or cells in the selected word line. A read pass voltage, e.g., 5 volts, can be applied to unselected word lines, e.g., to the control gates of cells in the unselected word lines. The drain to source current, e.g., the "cell current," or "drain current," flowing through cells on the selected word line, is indicative of the binary logic state of the cell.
As such, when the cell current of a particular memory cell is above the trip point, the memory cell is read as having a particular state, e.g., an erased state or a programmed state. When the cell current of the particular memory cell is below the trip point, the memory cell is read as having a different state. Therefore, a desired configured state of the memory cell, e.g., 00, 01, 10, or 11, depends on whether the cell current is above or below the trip point.
Memory cells having a state other than their desired/expected configured state, e.g., the state into which they were programmed, represent data errors in data being read. Many memory devices and/or systems employ an error checking technique such as error correction code (ECC) checking to detect bit errors in data, e.g., cells having incorrect states. The error correction codes can be associated with groups of cells, e.g., memory blocks, memory segments, or memory sectors, and can reduce read failures by detecting and possibly correcting bit errors. Examples of error correction codes include, Hamming codes, Reed-Solomon (RS) codes, Bose-Chaudhuri-Hochquenghem (BCH) codes, circular redundancy check (CRC) codes, Golay codes, Reed-Muller codes, Goppa codes, and Denniston codes, among others.
Read failures occur when accessed data bits, e.g., memory cells representing information retrieved by a processor, have incorrect states. Reducing read failures increases the operational reliability of memory devices and/or systems. Error checking/correcting techniques may not be able to correct more than a certain number of erroneous bits. Furthermore, many error checking techniques may not even be able to detect more than a particular number of erroneous bits for a given group of cells, e.g., a data word or data sector.
Therefore, the read failure rate increases as the number of memory cells having incorrect states increases. The state of a memory cell can be incorrect for several reasons. For example, floating gate to floating gate interference from adjacent cells can shift the Vt of a memory cell, which can in turn result in a modified cell current. This cell current modification can cause the cell to switch from a correct state to an incorrect state. The Vt shifts and associated cell current shifts caused by interference can have a greater effect on a cell programmed to the erased state when adjacent cells are programmed to higher data states. Vt shifts and cell current modification affect greater numbers of cells as cell read margins are reduced as scaling of memory devices shrinks in dimension, etc.

This patent is subject to a terminal disclaimer.


The present invention is directed to a method and system for use in a computing environment for representing files stored in stacks. The method includes providing a set of stack icons, each icon in the set having a stack height representing a range of stack sizes. The method additionally includes determining a stack size for a selected stack and selecting and displaying an appropriate stack icon from the set of stack icons based on the determined stack size. The selected stack may be stored within one of multiple libraries. Accordingly a distinct set of icons relevant to each library may be stored for each library. The icons may visibly convey information pertaining to the relevant library. Accordingly, the method may include representing a selected stack by determining an appropriate library and an appropriate stack height and displaying a corresponding icon. The system may additionally include an empty stack icon, a generic stack icon, property based icons, and custom thumbnail icons.

In current computer operating system environments, icons are provided for representing items such as files, folders, shortcuts, applications, documents, tasks, and commands. Icons may be used in list views, toolbars, dialog boxes, menus, and other places. Icons may be used to represent all objects of a specific class, such as Microsoft Word documents, Microsoft Excel files, jpeg files, or other types of files.
Icons may include thumbnail images used to represent specific objects, such as a specific jpeg or a specific folder. Icons may be dynamically generated by code run on a user's machine or may be cached. Icons have existed for many years and many applications use existing icon architectures. Application and component developers can, using custom icons and thumbnails, convey as much information about objects as their pixels will allow. However, existing systems do not provide a technique for graphically grouping multiple icons based on properties of the files represented.
Currently, when a user wants to group items having common characteristics, the user often groups the items into a folder. For example, a user can group documents by file type to include one group for Microsoft Word documents, one for Microsoft Excel documents, one for Microsoft PowerPoint documents, etc. A user may also group music by genre, creating separate groups for Pop, Classical, Hip-Hop, etc. While the conventional folder structure and icon may provide easy access to the documents, the generic folder icon fails to provide descriptive information pertaining to items within the folder.
A solution is needed for visually representing these groups to the user. The use of a generic icon such as the generic folder icon to represent groups of items has a number of shortcomings. First, using a generic icon to represent a group will not provide a user with any idea of how many items are in the group. In contrast, in a real-world stack view, a user is able to view an approximate number of items in the stack. It would be desirable to have an icon represent a real-world stack view in which the group of items could be viewed as a stack and in which a viewer can view the size of the stack and see relative stack sizes merely by viewing the stack. Additionally, a solution is needed that allows the user to see the types of items that the stack contains. Furthermore, a solution should be provided that is capable of conveying the concept of an empty stack.
Accordingly, a solution is needed for immediately conveying to a user the size of a stack and the character of items within the stack. The solution should allow users to view stacks of items and infer characteristics of the stack based on the representation of the stack.

System and method for displaying stack icons


A toy has a changing facial expression and includes a hollow toy body with a torso section and a head section on the torso section. The head section has a front side formed with a face opening. The torso section is provided with a pair of forwardly extending arms that are mounted pivotally on two sides thereof. The arms have distal ends that hold a shielding member therebetween, and are pivotable on the torso section between a lowered position, where the shielding member uncovers the face opening, and a raised position, where the shielding member extends across the face opening to cover the face opening. A face member is disposed rotatably in the head section of the toy body and is formed with at least two face sections. The face member can be rotated to move a previous one of the face sections from alignment with the face opening and register another one of the face sections with the face opening when the arms are in the raised position.

1. Field of the Invention
The invention relates to toys, more particularly to a toy with a changing facial expression.
2. Description of the Related Art
Numerous toys have been proposed in the past which have the ability to provide a changing facial expression. U.S. Pat. No. 4,294,033 teaches an animated talking doll with a mouth area that is movable between open and closed positions while air passes through a sounding mechanism to generate an audible sound. U.S. Pat. No. 4,710,145 teaches a therapeutic doll figure with eyes and a mouth that are attached removably on a head section of a doll body for altering the facial expression of the doll figure. U.S. Pat. No. 4,798,556 teaches an article which has a changeable-expression face and which includes three independently moveable facial components that are mounted rotatably on a facing plate and that correspond to a mouth and two eyes on a face of the article. U.S. Pat. No. 4,820,234 teaches a doll which includes a plurality of independent and exchangeable facial segments that are built upon a post to create a doll face, the facial segments having a plurality of expressions selectively and separately placed into view to effect mood changes. U.S. Pat. No. 4,900,289 teaches a mechanism for animating a doll's facial features which incorporates a motor for powering jaw, eye and eyelid motion. U.S. Pat. No. 5,407,376 teaches a voice-responsive doll eye mechanism for providing doll eye motion in response to a voice.


There is provided a control panel assembly and method of manufacturing the same. In the control panel assembly, a control panel is disposed at a front of the control panel assembly, a button is coupled with the control panel, and a light source is disposed at a back of the button to emit a light. The button includes a body member molded with copolymer, a painted part coated on a front of the body member with a colored painting material, and a character portion carved in the painted part.

1. Field of the Invention
The present invention relates to a control panel assembly, and more particularly, to a control panel assembly and method of manufacturing the same, which requires fewer manufacturing operations.
2. Discussion of the Related Art
Washing machine are widely used to clean laundry. The washing machine agitates the laundry together with water containing detergent by driving a pulsator or a drum. The washing machine can be classified into a pulsator type and a drum type, and the latter is being more widely used than the former because of its lower overall height and wrinkle-reducing characteristic.
The washing machine usually includes a front member with a control panel assembly. The control panel assembly is provided with a plurality of buttons on which characters are formed for the user to control the operation of the washing machine.
However, since the buttons of the control panel assembly are usually wet when the user operates the washing machine, the characters of the buttons are easily worn off when repeatedly touched.
Further, it is not easy for the user to manipulate the control panel assembly in a dark place.

Control panel assembly and method of manufacturing for the same


A scalp care composition directed to a scalp care composition comprising from about 0.05% to about 5% of an anti-dandruff active, from about 0.1% to about 25% of one or more organic solvents, from about 1% to about 99% of a volatile carrier wherein the anti-dandruff active is soluble in the scalp care composition.

Hair and scalp leave on treatment compositions comprising various combinations of hair and scalp actives, are known in the art and are commercially available. Anti-dandruff hair rinse off products are also commercially available. Anti-dandruff shampoos, conditioners, and other rinse off treatments typically incorporate an anti-dandruff active. One type of anti-dandruff agents are particulate, crystalline anti-dandruff agents, such as sulfur, selenium disulfide and transition metal salts of pyridinethione. Soluble anti-dandruff agents, such as climbazole, are also available.
Nevertheless, some consumers desire an anti-dandruff leave on treatment which provides a level of anti-dandruff efficacy that can replace other anti-dandruff rinse off products or be in addition to rinse off anti-dandruff products or provide leave on benefits to hair and scalp that are difficult to achieve with a rinse off product. Consequently, a need exists for a treatment product that combines core anti-dandruff efficacy with additional scalp health and hair benefits that the consumer can notice and feel, i.e. effective, and is delightful to use.
It has now been surprisingly discovered that the incorporation of certain formulation solvents can increase the anti-fungal potency of a given composition. These, and other objects, will become readily apparent from the detailed description below.


An apparatus for manufacturing a decorated molded product includes a first clamping device for pressing an insert film to a parting face of a fixed mold to enclose a cavity and an injection gate. The fixed mold has a vacuum suction port and the injection gate for a molten resin. A movable mold has a runner facing the injection gate and communicating with the cavity. The insert film is held between the fixed mold and movable mold, so that a pattern of the insert film is formed to a molded product simultaneously when the product is injection-molded. The insert film after being pressed to a surface of the fixed mold by the first clamping device is brought into tight contact with the fixed mold by vacuum suction, and the molten resin is injected from the injection gate to pass through the runner of the movable mold from a hole formed in the insert film to finally reach the cavity and fill a gap between the insert film and movable mold.

There has been conventionally executed a technique whereby a decorated molded product is manufactured by a transfer molding method wherein a decoration pattern on a transfer film held between fixed and movable molds is transferred through a transfer method to a molded object simultaneously with injection molding of the object. Since a resin is injected from the side of the fixed mold in the above technique, generally, the transfer film is held in tight contact with the movable mold, so that-the resin is filled between the transfer film and the fixed mold.
Meanwhile, in some cases, the resin is filled between the movable mold and the transfer film which is kept in touch with the fixed mold although the resin is similarly injected from the fixed mold as above. For example, as disclosed in the published specification of Unexamined Japanese Patent Laid-Open Publication No. 59-194848, holes are formed in the transfer film taken out from a coil and the resin is injected and filled from the fixed mold to a gap between the movable mold of a molding part and the transfer film through the holes of the transfer film. The holes of the transfer film are formed in any of the following methods: (1) A hole formation device is set in the fixed mold, and the transfer film is cut by a blade after clamping of the molds, whereby holes of a size passing the resin are formed; (2) The transfer film is pierced and broken by an injection nozzle after clamping of the molds; (3) The transfer film is pierced and broken with a pressure of the resin injected after clamping of the molds.
All of the above methods have problems.
Specifically, when the transfer film is cut, a large amount of cutting dust is mixed into the molten resin. The cutting dust is also accumulated thereby to clog an opening part of a runner. Moreover, the cutting dust is accumulated at parting faces thereby to damage the molds. Since the hole formation device is buried in the mold, the mold is complicated and bulky in structure, which miniaturizes a cavity. The method is poor in practical utility.
According to the methods (2) or (3), the transfer film is forcibly broken by the injection nozzle or molten resin, and therefore it is impossible to surely open small holes in the transfer film. Even when the hole is opened, a large broken tongue-like piece of the film tightly adheres to the movable mold, clogging the opening part of the runner in the movable mold and obstructing the molten resin in flowing.
An object of the present invention is to solve the aforementioned problems and provide an apparatus and a method for manufacturing decorated molded products whereby the generation of cutting dust is restricted and a small hole is surely formed in an insert film to pass a molten resin.

Apparatus for molding patterned product and method of molding patterned product