KR101541989B1 - Mold release agent composition and transfer foil using same - Google Patents

Abstract

The present invention relates to a composition for an aminoalkyd resin, a hydrocarbon-based polymer having two or more hydroxyl groups, and a release agent containing an acid, and a transfer foil having a release layer formed using the composition.

Description

MOLD RELEASE AGENT COMPOSITION AND TRANSFER FOIL USING SAME <br> <br> <br> Patents - stay tuned to the technology MOLD RELEASE AGENT COMPOSITION AND TRANSFER FOIL USING SAME

The present invention relates to a release agent composition useful as a material for a release layer of a transfer foil and a transfer foil having a release layer formed using the composition.

A decorative article is produced by using a transfer foil in which a decorative layer having characteristics such as design, scratch resistance and antistatic property is formed on a substrate film having releasability by a vacuum press transfer method or an in-mold transfer method, A pattern printing is performed on the three-dimensional shape surface of the printed circuit board, and various characteristics are given.

0 to 40 parts by weight of a plasticizer is added to one side of a vinyl chloride resin layer having a thickness of 10 to 500 占 퐉 and made of a vinyl chloride resin having an average polymerization degree of 1,500 or less and a water soluble polyester, polyvinyl alcohol, ethylene vinyl There is known a release film for a transfer film comprising a release layer made of a resin selected from an alcohol copolymer resin, an ultraviolet ray-curable acrylic resin and an ultraviolet ray-curable silicone resin and having a thickness of 0.5 to 50 탆. By using this film, It is possible to obtain a transfer foil satisfactorily conforming to the drawing shape and having excellent releasability from the decorative layer (see Patent Document 1).

A transfer material comprising a releasing agent layer made of a room temperature curing resin, a pattern layer and an adhesive layer successively formed on a base sheet made of an unstretched polyester resin is known, and as the room temperature curing resin, butylated urea melamine water A coating solution obtained by blending an acid-curable resin such as an acid-curing aminoalkyd cocondensed resin with an acidic solution such as para-toluene sulfonic acid, or a curable resin such as a polyurethane resin. The use of this transfer material makes it possible to adhere to the surface of a not-yet-raised transfer object without gaps, so that a wrinkled pattern is formed, a pattern layer is formed freely from the surface of the transferred object, (See Patent Document 2).

Japanese Unexamined Patent Publication No. 8-20199 Japanese Patent Application Laid-Open No. 9-123694

It has been known that a transfer foil using an amino alkyd resin as a release agent can be easily transferred to a deep drawing shaped article as described above. However, depending on the type of the transfer layer, More specifically, there has been a problem in that cracks are generated in the transfer layer (decorative layer) transferred to the surface of the molded article.

It is another object of the present invention to provide a transfer sheet which does not cause cracks in the transfer layer when the transfer sheet is subjected to deep drawing.

The inventors of the present invention have made extensive studies in order to solve the above problems. As a result, they found that cracks are generated in the releasing layer at the time of in-mold forming due to cracks in the transfer layer after transfer, It is possible to solve the above problems by studying a composition in which cracks are not formed in the layer. Thus, the present invention has been completed.

That is,

An aminoalkyd resin, a hydrocarbon-based polymer having two or more hydroxyl groups, and a release agent containing an acid.

In the composition for a mold release agent of the present invention, the aminoalkyd resin is preferably an aminoalkyd resin containing a long-chain alkyl group, and the hydrocarbon-based polymer having two or more hydroxyl groups is preferably a poly Butadiene polyol, and the weight average molecular weight of the hydrocarbon polymer having two or more hydroxyl groups is preferably in the range of 1,500 to 2,500.

The present invention also relates to a transfer foil obtained by coating the release agent composition on a release layer of a transfer foil comprising a substrate, a release layer, and a transfer layer.

In the transfer foil of the present invention, it is preferable that the transfer layer has a structure in which a) an organic silicon compound and / or condensate thereof represented by the following formula (I), b) an ultraviolet curable compound, and c) Is preferred.

[Chemical Formula 1]

(Wherein R represents an organic group in which a carbon atom is directly bonded to Si in the formula, X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and when n is 2, two R May be the same or different, and when (4-n) is 2 or more, plural Xs may be the same or different.

By using the release agent composition of the present invention or a transfer foil using the composition, it is possible to transfer without forming a crack in the transfer layer even in the case of a deep drawing shaped article.

The release agent composition of the present invention contains an aminoalkyd resin, a hydrocarbon-based polymer having two or more hydroxyl groups, and an acid.

The aminoalkyd resin used in the release agent composition of the present invention is obtained by curing an alkyd resin by mixing a curing component such as an amino resin. The alkyd resin may be a known one, but it has an oil length of 0 to 60, preferably 5 to 60, more preferably 20 to 40, and an acid value of 1 to 30 mgKOH / g, Coconut fatty acid, soybean oil, soybean oil fatty acid, castor oil, or castor oil fatty acid having a hydroxyl value of 50 to 300 mgKOH / g, preferably 100 to 250 mgKOH / g, . The alkyd resin may be modified with an acrylic resin, a polyester resin, an epoxy resin, a phenol resin or the like, or may be used in combination.

The amino resin refers to a resin obtained by a condensation reaction of an aldehyde with a compound containing an amino group, and includes aniline aldehyde resin, urea resin, melamine resin and the like. As the amino resin, various commercially available amino resins may be used, or may be synthesized according to a known method. As the synthesizing method, for example, various amino resins synthesized using a prepolymer containing methylol or its ether as a raw material resin can be used. More specifically, various known resins such as a methylated melamine resin, a butylated melamine resin, a methylated urea resin, a butylated urea resin, a methylated benzoguanamine resin, and a butylated benzoguanamine resin can be used. It is particularly preferable to use a methylated melamine resin, particularly a methylated melamine resin containing at least one triazine nucleus, as a main component.

The aminoalkyd resin to be used in the present invention is not particularly limited as long as it is the one described above, but an aminoalkyd resin containing a long-chain alkyl group containing an alkyl group having about 7 to 30 carbon atoms is preferable.

Examples of the hydrocarbon-based polymer having two or more hydroxyl groups used in the release agent composition of the present invention include polyolefin-based polyols such as polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol, . Among them, polybutadiene polyol is particularly preferable, and its weight average molecular weight is not particularly limited, but is preferably in the range of 1500 to 2500. The ratio of 1,2-bond and 1,4-bond is not particularly limited, but the ratio of 1,2-bond is preferably 70% or more, and more preferably 80% or more.

POLY bd R-45HT "(hydroxyl value = 45.4 mg KOH / g, Mn = 2470, oxygen content 2.57% by mass) manufactured by Idemitsu Kosan Co., Ltd., trade name" NISSO PB- 2000 &quot; (hydroxyl group = 35-55 mgKOH / g).

The mixing ratio of the aminoalkyd resin and the hydrocarbon-based polymer having two or more hydroxyl groups (aminoalkyd resin / hydrocarbon-based polymer having hydroxyl group having two or more hydroxyl groups) is not particularly limited, but is preferably in the range of 60/40 to 90/10 And is preferably in the range of 70/30 to 80/20.

Examples of the acid used in the release agent composition of the present invention include carboxylic acids such as acetic acid, formic acid, oxalic acid, tartaric acid and benzoic acid, and organic acids such as sulfonic acids such as toluenesulfonic acid, dodecylbenzenesulfonic acid, ; Minerals such as hydrochloric acid, nitric acid, and boric acid; And an organic acid is preferable.

The releasing layer may be formed by dispersing or dissolving the resin in a solvent and coating on the substrate by a printing method such as a gravure coating method, a roll coating method, a comma coating method, a lip coating method, a gravure printing method, Followed by drying and baking at a temperature of about 150 ° C to 200 ° C. The thickness of the release layer is usually about 0.01 탆 to 5.0 탆, preferably about 0.1 탆 to 2.0 탆.

Further, when the release layer is formed, the surface of the base material may be subjected to a corona treatment or an adhesion facilitating treatment.

As the substrate used in the transfer foil of the present invention, various materials may be used depending on the application, provided that it has heat resistance, mechanical strength to withstand manufacture, and solvent resistance. Specific examples thereof include polyethylene terephthalate, polybutylene terephthalate Based resins such as polyamide-based resins and polyvinyl chloride; acrylic resins; imide resins; engineering resins such as polyarylates; polycarbonates; cyclic polyolefin resins; And cellulose-based films such as cellophane. The base material may be a copolymer resin containing these resins as a main component, a mixture (including a polymer alloy), or a laminate composed of a plurality of layers. Normally, polyester films such as polyethylene terephthalate and polyethylene naphthalate are preferably used because they have good heat resistance and mechanical strength, and polyethylene terephthalate is the most suitable.

The base material may be a stretched film or an unoriented film, but a film stretched in the uniaxial or biaxial direction is preferable for the purpose of improving the strength. The thickness of the substrate is usually about 10 to 100 mu m, preferably 20 to 50 mu m, and most preferably 35 to 40 mu m. The base material is applied to the application surface prior to application by a corona discharge treatment, a plasma treatment, an ozone treatment, a frame treatment, a primer treatment (anchor coat, adhesion promoter, An easy adhesion treatment such as an alkali treatment may be performed. If necessary, additives such as a filler, a plasticizer, a colorant, and an antistatic agent may be added.

The transfer layer used in the transfer foil of the present invention is not particularly limited, and specifically, a hard coat layer which is a surface protective film can be preferably exemplified. As the transfer layer, specifically, a layer containing an organic-inorganic hybrid substance containing a) an organosilicon compound represented by the following formula (I) and / or a condensate thereof, b) an ultraviolet curable compound, and c) a silanol condensation catalyst Can be exemplified.

(2)

When the silanol condensation catalyst is a metal catalyst, a) and c) may be unbonded to each other, one side may be dispersed in the other, or they may be chemically bonded to each other. For example, it may be one having a Si-O-M bond (wherein M represents a metal atom in the silanol condensation catalyst) or a mixed state thereof.

a) Organosilicon compound

Among the organosilicon compounds represented by the formula (I), R and X are each as follows.

R represents an organic group in which a carbon atom is directly bonded to Si in the formula. Examples of such an organic group include a hydrocarbon group which may have a substituent, and a group which is composed of a polymer of a hydrocarbon which may have a substituent.

As the hydrocarbon group, a hydrocarbon group of 1 to 30 carbon atoms which may have a substituent is preferable, and an alkyl group of 1 to 10 carbon atoms which may have a substituent, an alkenyl group of 2 to 10 carbon atoms which may have a substituent or an epoxy group of 1 to 10 carbon atoms An alkyl group is more preferred.

The organic group may contain a silicon atom or may contain a polymer such as polysiloxane, polyvinylsilane, or polyacrylsilane.

Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and the like.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a butyl group, a butyl group, an isobutyl group, an amyl group, an isoamyl group, a tertiary amyl group, a hexyl group, a cyclohexyl group, a cyclohexylmethyl group, Heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl and the like, preferably an alkyl group having 1 to 10 carbon atoms.

Examples of the alkenyl group include vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl and tricosenyl. Group is preferable.

Examples of the substituent of the "hydrocarbon group which may have a substituent (s)" include a halogen atom, an alkoxy group, an alkenyloxy group, an alkenylcarbonyloxy group and an epoxy group.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert- 1-methylbutoxy, n-hexyloxy, isohexyloxy, 4-methylpentoxy and the like, and an alkoxy group having 1 to 10 carbon atoms is preferable.

The alkenyloxy group is a group in which an alkenyl group having a carbon-carbon double bond at one or more positions and an alkyl group are bonded through an oxygen atom, and examples thereof include vinyloxy, 2-propenyloxy, 3- Pentyloxy, 4-pentenyloxy and the like, and an alkenyloxy group having 2 to 10 carbon atoms is preferable.

Examples of the alkenylcarbonyloxy group include groups in which an alkenyl group is bonded to a carbonyloxy group, and examples thereof include acryloxy, methacryloxy, allylcarbonyloxy, 3-butenylcarbonyloxy and the like, An alkenylcarbonyloxy group is preferred.

Examples of the hydrocarbon group having an epoxy group as a substituent include epoxyethyl, 1,2-epoxypropyl, glycidoxyalkyl, epoxycyclohexylethyl and the like.

When R is a group composed of a polymer, examples of the hydrocarbon polymer which may have a substituent include a methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate such as hexyl (meth) acrylate; Acid anhydrides such as carboxylic acids such as (meth) acrylic acid, itaconic acid, and fumaric acid, and maleic anhydride; Epoxy compounds such as glycidyl (meth) acrylate; Amino compounds such as diethylaminoethyl (meth) acrylate and aminoethyl vinyl ether; Amide compounds such as (meth) acrylamide, itaconic acid diamide,? -Ethyl acrylamide, crotonamide, fumaric acid diamide, maleic acid diamide and N-butoxymethyl (meth) acrylamide; Vinyl compounds selected from acrylonitrile, styrene,? -Methylstyrene, vinyl chloride, vinyl acetate, and vinyl propionate; Vinyl-based polymers obtained by copolymerizing vinyl polymers.

n represents 1 or 2, and n = 1 is more preferable. When n is 2, the two Rs may be the same or different.

X represents a hydroxyl group or a hydrolyzable group. When (4-n) in the formula (I) is 2 or more, X may be mutually the same or different. The hydrolyzable group means, for example, a group capable of hydrolyzing to form a silanol group or a siloxane condensate by heating at 25 ° C to 100 ° C in the presence of an uncatalyzed or excess water, Specific examples include an alkoxy group, an acyloxy group, a halogen atom and an isocyanate group, and an alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 4 carbon atoms is preferable.

Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group and t- Examples of the acyloxy group include acyloxy groups such as formyloxy, acetyloxy and propanoyloxy.

Specific examples of the organosilicon compound include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane , Butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, (Meth) acryloxypropyltrimethoxysilane, gamma -glycidoxypropyltrimethoxysilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane, trimethylchlorosilane, vinyltrimethoxysilane, 3- Methyl (meth) acryloxysilane, methyl [2- (meth) acrylate, methyl (meth) acrylate, ) Acryloxyethoxy ] Silane, methyl-may be mentioned triglycidyl oxy-silane, methyl-tris (3-methyl-3-oxetanyl methoxy) silane.

These may be used alone or in combination of two or more.

When the organosilicon compound is used in combination, for example, a combination of vinyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane, a combination of vinyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane Combinations can be preferably exemplified.

These organosilicon compounds may be condensation products. Condensates specifically include, for example, dimers obtained by hydrolysis and condensation of the above-mentioned organosilicon compounds to form siloxane bonds.

It is preferable that the organosilicon compound represented by the formula (I) and / or the condensate thereof has a carbon number of 3 or less, and that the proportion of the compound represented by the formula (I) and / or its condensate is 30 mol% And more preferably 50 mol% or more. It is preferable that the number of carbon atoms of R is 4 or more and that the amount of R is 5 mol% or more based on the compound represented by formula (I) and / or the condensate thereof.

In other words, it is preferable that 30 to 95 mol% of the R's have 3 or less carbon atoms, 5 to 70 mol% of the R's have 4 or more carbon atoms, more preferably 50 to 95 mol% Is in the range of 5 to 50 mol%.

b) UV curable compound

The ultraviolet curing compound of the present invention is a compound which is polymerized by irradiation with active energy rays. Particularly, a compound or resin having a functional group which causes a polymerization reaction by irradiation of ultraviolet rays in the presence of a photopolymerization initiator, and a vinyl compound other than a (meth) acrylate compound, an epoxy resin and an acrylate compound. The number of functional groups is not particularly limited as long as it is one or more.

Examples of the acrylate compound include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, polybutadiene Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, (trimethylolpropane tri (meth) acrylate, (Meth) acryloyloxy group, and the like. Of these, preferred are a polyester (meth) acrylate, a polyurethane (meth) acrylate and an epoxy (meth) acrylate, and more preferably a polyurethane Meth) acrylate.

The molecular weight is not limited so long as it has compatibility with other hard coat layer compositions, but usually the weight average molecular weight is 500 to 50,000, preferably 1,000 to 10,000.

The epoxy (meth) acrylate can be obtained, for example, by an esterification reaction of an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolac epoxy resin with acrylic acid.

The polyester (meth) acrylate is obtained, for example, by esterifying a hydroxyl group of a polyester oligomer having hydroxyl groups at both terminals, which is obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol, with acrylic acid. Or by esterifying an end hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with acrylic acid.

The polyurethane (meth) acrylate is a reaction product of an isocyanate compound obtained by reacting a polyol and a diisocyanate and an acrylate monomer having a hydroxyl group. Examples of the polyol include polyester polyol, polyether polyol, polycarbonate diol .

Examples of commercial products of the polyurethane (meth) acrylate used in the present invention include trade names of Beam Set 102, 502H, 505A-6, 510, 550B, 551B, 575 and 575CB manufactured by Arakawa Chemical Industries, , EM-90, EM92; Trade names: Photomer 6008, 6210, manufactured by Sanofovak Co., Ltd.; U-4H, U-6HA, H-15HA, UA-32PA, U-324A, U-4H, U-6H manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade names: NK Oligo U-2PPA, Aronix M-1100, M-1200, M-1210, M-1310, M-1600, M-1960, AH-600, AT606, UA-306H manufactured by Kyowa Chemical Industry Co., Ltd.; UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101 manufactured by Nippon Kayaku Co., UV-7600B, UV-7600B, UV-7600B, UV-7600B, UV-7600B, UV-7600B, UV-7610B, UV-7630B, UV-7600B manufactured by Nippon Synthetic Chemical Industry Co., 7550B; UN-3320HB, UN-3320HB, UN-9010M, UN-904M, UN-902M, UN- 3320HC, UN-3320HS, H-61, HDP-M20; Ebecryl 6700, 204, 205, 220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866, 5129, 6602, 8301, manufactured by Daicel UCB Co., ACA200M, ACAZ230AA, ACAZ250, ACAZ300, ACAZ320 manufactured by Daicel-Cytec Co., Ltd.; And the like.

Examples of the vinyl compound other than the acrylate compound include N-vinylpyrrolidone, N-vinylcaprolactam, vinyl acetate, styrene, and unsaturated polyester. Examples of the epoxy resin include hydrogenated bisphenol A diglycidyl Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-methane -Dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, and the like.

Examples of the photopolymerization initiator include (i) a compound which generates a cationic species by light irradiation and (ii) a compound which generates an active radical species by light irradiation.

As a compound capable of generating a cationic species by light irradiation, for example, an onium salt having a structure represented by the following formula (II) is a preferable example. This onium salt is a compound which releases Lewis acid by receiving light.

(3)

Equation (Ⅱ) wherein cation is an onium ion, W is, S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N≡N-, R ^1, R ² , and R ³ and R ⁴ are the same or different organic group, a, b, c, and d is an integer of 0 to 3, respectively, (a + b + c + d) is equal to the valence of W. M is a central atom of the halide complex [ML _{e + f} ], for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, Mn, and Co. L is, for example, a halogen atom such as F, Cl, or Br, e is the net charge of the halide complex ion, and f is the valence of M.

Specific examples of the anion (ML _{e + f} ) in the formula (II) include tetrafluoroborate (BF ₄ ^- ), hexafluorophosphate (PF ₆ ^- ), hexafluoroantimonate (SbF ₆ ^- ), Hexafluoroarsenate (AsF ₆ ^- ), and hexachloroantimonate (SbCl ₆ ^- ).

An onium salt having an anion represented by the formula [ML _f (OH) ^- ] may also be used. Other examples of the perchlorate ion (ClO ₄ ^- ), trifluoromethanesulfonate ion (CF ₃ SO ₃ ^- ), fluorosulfonate ion (FSO ₃ ^- ), toluenesulfonate ion, trinitrobenzenesulfonate anion and trinitrotoluenesulfonate anion Or an onium salt having an anion. These may be used alone or in combination of two or more.

Examples of the compound capable of generating an active radical species by light irradiation include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane- 1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, Benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2- ) Phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzo Trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methyl Vinyl) phenyl) propanone).

The blending amount of the photopolymerization initiator used in the present invention is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the solids content of the ultraviolet curing compound such as (meth) acrylate.

In the present invention, a sensitizer may be added if necessary. Examples of the sensitizer include trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, p-dimethylaminobenzoate, p- Aminobenzoic acid isoamyl, N, N-dimethylbenzylamine and 4,4'-bis (diethylamino) benzophenone.

The ultraviolet curable compound is preferably 80% by mass or less based on the total mass of the solid content of the composition for forming a transfer layer.

c) a silanol condensation catalyst

The silanol condensation catalyst is not particularly limited as long as the hydrolyzable group in the compound represented by the formula (I) is hydrolyzed and the silanol is condensed to form a siloxane bond. Examples of the silanol condensation catalyst include organic metal, organic acid metal salt, acid, base, metal chelate compound And the like. The silanol condensation catalyst may be used alone or in combination of two or more.

Specific examples of the organic metal include organic titanium compounds such as alkyl titanates such as tetraisopropoxy titanium, tetrabutoxy titanium and titanium bisacetylacetonate; And alkoxyaluminum.

Examples of the organic acid metal salt include zinc octanoate, lead 2-ethylhexanoate, dibutyltin diacetate, dibutyltin dileate, stannous octanoate, zinc naphthenate and ferrous octanoate, tin octylate, Dibutyltin dicarboxylate and the like, carboxylic acid alkali metal salts, and carboxylic acid alkaline earth metal salts.

Specific examples of the acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid and the like as the organic acid, and hydrochloric acid , Nitric acid, boric acid, and hydrofluoric acid.

The acid includes a photoacid generator that generates an acid upon irradiation with light, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like.

Examples of the base include strong bases such as tetramethylguanidine and tetramethylguanidylpropyltrimethoxysilane; Organic amines, carboxylic acid neutralized salts of organic amines, quaternary ammonium salts and the like.

Examples of the metal chelate compound include aluminum chelates, and specific examples thereof include those shown below.

[Chemical Formula 4]

In the formula, acac represents an arity acetonate group, Pr represents a propyl group, Bu represents a butyl group, and Et represents an ethyl group.

These may be used singly or in combination of two or more.

As the silanol condensation catalyst, a photosensitive compound capable of removing the carbon component on the surface side by the action of light having a wavelength of 350 nm or less is preferable.

The photosensitive compound is a compound capable of removing the carbon component on the surface side by the action of light having a wavelength of 350 nm or less irradiated from the surface side irrespective of the mechanism thereof and is preferably a compound having a refractive index of 2 nm Is 80% or less of the carbon content of the portion where the amount of carbon is not reduced (in the case of the film, for example, the back surface portion in the depth direction 10 nm from the back surface of the film) 60%, more preferably 2 to 40%. Particularly preferably, a compound capable of removing the carbon component to a predetermined depth so as to gradually decrease the removal amount from the surface side, that is, Refers to a compound capable of forming a layer whose carbon content gradually increases to a depth. Specifically, for example, a compound that absorbs and excites light having a wavelength of 350 nm or less can be given.

Here, the light having a wavelength of 350 nm or less is light composed of light using light having a wavelength of 350 nm or less as a component, preferably light using a light source having a wavelength of 350 nm or less as a main component , That is, light having the largest component amount and using a light source having a wavelength of 350 nm or less.

Examples of the photosensitive compound that can be contained in the transfer layer of the present invention include a metal chelate compound, a metal organic acid salt compound, a metal compound having two or more hydroxyl groups or hydrolysable groups, a hydrolyzate thereof, and a condensate thereof Is preferably at least one kind of compound selected from the group consisting of hydrolysates and / or condensates, and more preferably hydrolyzates and / or condensates of metal chelate compounds. As the compound derived from this, for example, a condensate of a metal chelate compound or the like is further condensed. As described above, the photosensitive compound and / or the derivative thereof may be chemically bonded to the organosilicon compound, may be dispersed in a non-bonded state, or may be in a mixed state.

The metal chelate compound is preferably a metal chelate compound having a hydroxyl group or a hydrolyzable group, and more preferably a metal chelate compound having at least two hydroxyl groups or hydrolyzable groups. The term "having two or more hydroxyl groups or hydrolyzable groups" means that the sum of hydrolyzable groups and hydroxyl groups is two or more. The metal chelate compound is preferably a? -Ketocarbonyl compound, a? -Ketoester compound, and an? -Hydroxy ester compound. Specific examples thereof include methyl acetoacetate, n-propyl acetoacetate, acetoacetic acid ? -Keto esters such as isopropyl, n-butyl acetoacetate, sec-butyl acetoacetate, and t-butyl acetoacetate; Heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5-methyl- ,? -Diketones such as 4-dione; Hydroxycarboxylic acids such as glycolic acid and lactic acid; And the like.

The metal organic acid salt compound is a compound comprising a metal ion and a salt obtained from an organic acid. Examples of the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid and benzoic acid; Sulfuric acid, sulfuric acid, sulfinic acid, and thiophenol; Phenolic compounds; Enol compounds; Oxime compounds; Imide compounds; Aromatic sulfonamides; And the like.

The metal compound having two or more hydroxyl groups or hydrolysable groups excludes the metal chelate compound and the metal organic acid salt compound, and examples thereof include a metal hydride, a metal alcoholate, and the like.

Examples of the hydrolyzable group in the metal compound, the metal chelate compound or the metal organic acid salt compound include an alkoxy group, an acyloxy group, a halogen group and an isocyanate group. Examples of the hydrolyzable group include an alkoxy group having 1 to 4 carbon atoms, An acyloxy group having 1 to 4 carbon atoms is preferable. The term "having two or more hydroxyl groups or hydrolyzable groups" means that the sum of hydrolyzable groups and hydroxyl groups is two or more.

The hydrolyzate and / or condensate of such a metal compound is preferably hydrolyzed with 0.5 mole or more of water per 1 mole of the metal compound having two or more hydroxyl groups or hydrolysable groups, preferably 0.5 to 2 And more preferably hydrolyzed using molar water.

The hydrolyzate and / or condensate of the metal chelate compound is preferably hydrolyzed with 5 to 100 moles of water per mole of the metal chelate compound, preferably 5 to 20 moles of water It is more preferable that it is hydrolyzed.

The hydrolyzate and / or condensate of the metal organic acid salt compound is preferably hydrolyzed using 5 to 100 moles of water per mole of the metal organic acid salt compound, more preferably 5 to 20 moles of water It is more preferable that it is hydrolyzed.

Examples of metals in these metal compounds, metal chelate compounds or metal organic acid salt compounds include titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead. Of these, titanium, zirconium and aluminum are preferable, and titanium is particularly preferable.

In the present invention, when two or more silanol condensation catalysts are used, they may contain the compound having the above-described photosensitivity, or may not contain a compound having photosensitivity. In addition, a compound having photosensitivity and a compound having no photosensitivity may be used in combination.

Further, tetrafunctional silane or colloidal silica may be added to the transfer layer for the purpose of improving the hardness. Examples of the tetrafunctional silane include tetraaminosilane, tetrachlorosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrabenzyloxysilane, tetraphenoxysilane, tetra (Meth) acryloxy silane, tetrakis [2- (meth) acryloxyethoxy] silane, tetrakis (2-vinyloxyethoxy) silane, tetraglycidyloxysilane, tetrakis Silane, and tetrakis (3-methyl-3-oxetanemethoxy) silane. Examples of the colloidal silica include water-dispersed colloidal silica, and organic solvent-dispersed colloidal silica such as methanol or isopropyl alcohol.

The transfer foil of the present invention also contains the transfer layer having a semi-hardened state. The semi-cured state means a compound in which an organosilicon compound and / or an ultraviolet curable compound are partially condensed. The condensate is mainly a condensate of an organosilicon compound.

(Warrior Park)

A decorative layer (transfer layer) such as a release layer, a primer layer, a pattern layer or a metal deposition layer, an adhesive layer and the like may be laminated on the base material, if necessary, and preferably have an adhesive layer.

(Adhesive layer)

It is preferable that an organic resin adhesive layer is formed on the transfer layer in order to facilitate the transfer and firmly adhere the transfer layer after the transfer to the adherend (transfer object). As the adhesive layer, an acrylic resin, an acryl urethane resin, an acrylic vinyl acetate resin, an acryl styrene resin, a vinyl acetate resin, a polyolefin resin, a vinyl chloride resin and the like can be given. As the transfer foil, it is preferable that the glass transition temperature of the resin used is not lower than the room temperature so as not to be blocked after winding.

In addition, in order to form the organic resin adhesive layer on the transfer layer, it is preferably formed by applying an aqueous organic resin as a raw material, and drying it. A water-based organic resin solution, and is an organic resin solution prepared by dissolving an acrylic resin, an acrylic / urethane emulsion, an acrylic / vinyl acetate copolymer emulsion, an acryl / styrene copolymer emulsion, a vinyl acetate copolymer emulsion, an ethylene copolymer emulsion, Resins, aqueous urethane resins, vinyl chloride synthetic resins, and the like. Specific examples of the commercially available products include commercially available products such as Movinil 7980, 972, 760H, 081F, 082, 109E, 172E, 180E, 206, DC, 502N manufactured by Nichigo Movinyl Co., Manufactured by UNITICA CO., LTD., Product name: SF Primer W-123K, W-125A, W-200A, Hydran ADS-110, ADS-120, HW-311, HW-333, AP-20, APX-101H, AP-60LM HC-12, HC-17, and HC-38 manufactured by Nichia Chemical Co., Ltd. under the trade names of Aroo Base SA-1200, SB-1200, SE-1200, SB-1010 and SBN- And the like.

(Releasing layer)

The releasing layer can be obtained by coating the releasing agent composition of the present invention on a substrate or the like. The aminoalkyd resin, the hydrocarbon polymer having two or more hydroxyl groups, and components other than the acid may be appropriately added to the release agent composition of the present invention. As such a component, a releasable resin, a resin containing a release agent, and a curable resin which is crosslinked by ionizing radiation can be applied. The releasable resin is, for example, a fluororesin, a silicone resin, a melamine resin, an epoxy resin, a polyester resin, an acrylic resin, a fluorine-based resin, or the like. The resin containing the releasing agent is, for example, an acrylic resin, a vinyl resin, a polyester resin, a fiber-based resin or the like to which a releasing agent such as a fluorine resin, a silicone resin or various waxes is added or copolymerized.

The releasing layer can be formed by a method such as a coating method such as a gravure coating method, a roll coating method, a comma coating method and a lip coating method, a gravure printing method, a screen printing method, etc. , Followed by coating and drying. If necessary, crosslinking may be carried out by heat drying or aging at a temperature of 150 ° C to 200 ° C, or by irradiation with an active energy ray. The thickness of the release layer is usually about 0.01 μm to 5.0 μm, preferably about 0.1 μm to 2.0 μm.

Further, when the release layer is formed, the surface of the base material may be subjected to a corona treatment or an adhesion facilitating treatment.

In addition to the above-described layers, a transfer layer may be formed with a pattern layer and / or a metal vapor deposition layer.

The thickness of the transfer layer in the semi-cured state varies depending on the application, but it is preferable that the thickness of the transfer layer in the semi-cured state before transfer is 0.5 to 20 mu m, particularly about 1 to 10 mu m.

Various additives such as an antistatic agent, a water repellent agent, a oil repellent agent, a stabilizer, a conductive agent, an antifogging agent and the like may be added to each layer as long as the physical properties and functions of each layer are not inhibited .

(Production method of transfer foil)

The production of the transfer foil of the present invention can be carried out by laminating each layer on a substrate, but any known lamination method can be used. For example, each layer can be formed by methods such as microgravure coating, comma coating, bar coater coating, air knife coating, offset printing, flexo printing, screen printing, spray coating and the like.

The semi-cured state transfer layer to the base material is formed by applying a liquid containing the composition for forming a transfer layer on the base material, followed by semi-curing by heating and / or irradiation with active energy rays. By this step, the condensate of the organosilicon compound in the transfer layer forming composition is crosslinked, and the hard coat layer is semi-cured. When an organic solvent is used as a diluting solvent or the like, the organic solvent is removed by this heating. The heating is usually 40 to 200 占 폚, preferably 50 to 150 占 폚. The heating time is usually 10 seconds to 30 minutes, preferably 30 seconds to 5 minutes.

(How to use transfer foil)

The transfer foil of the present invention can be used in known conditions and methods. For example, the transfer foil and the adherend (transferred object) are closely contacted and transferred.

The material to be adhered is not limited, and examples thereof include resin molded products, woodwork products, and composite products thereof. These may be transparent, translucent, or opaque. The adherend may be colored or not colored. Examples of the resin include general-purpose resins such as polystyrene-based resin, polyolefin-based resin, ABS resin and AS resin. Examples of the resin include polyphenylene oxide, polystyrene resin, polycarbonate resin, polyacetal resin, acrylic resin, polycarbonate modified polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, ultra high molecular weight polyethylene resin Polyphenylene sulfide resin, polyphenylene oxide resin, polyacrylate resin, polyetherimide resin, polyimide resin, liquid crystal polyester resin, and polyallyl heat-resistant resin. A super engineering resin may also be used. A composite resin to which a reinforcing material such as glass fiber or inorganic filler is added may also be used.

As a method of forming the transfer layer on the surface of the adherend, for example, a transfer foil is adhered to the surface of the adherend, and then the substrate (per release layer) of the transfer foil is peeled off, (Transfer method) in which the resin is cured by irradiation with active energy rays and, if necessary, by heating (transfer method); or a method in which the transfer foil is fitted into a molding die and the resin is injected into the cavity to obtain a resin molded article, A method in which a transfer foil is adhered to the surface, the base material (for each release layer) is peeled off and transferred onto a molded product, and then curing is performed by active energy ray irradiation and, if necessary, heating.

A method for forming a hard coat layer of a molded article by an in-mold transfer method will be described in detail. First, a semi-hardened transfer layer is set inside a mold for a movable mold and a stationary mold, And transferring the transfer foil to the surface. At this time, one transfer sheet of each sheet may be fed one by one, and a necessary portion of the long transfer sheet may be fed intermittently. After the molding die is closed, the molten resin is injected from the gate formed in the movable die into the mold to form a molded product, and the transfer foil is adhered to the surface. After cooling the resin molded article, the molding mold is opened to take out the resin molded article. Finally, after peeling the substrate (for each release layer), the transfer layer is completely cured by irradiation with active energy rays and heating as required.

The transferring and curing step of the semi-cured transfer layer may be carried out by transferring the transfer foil onto the surface of the molded article by adhering the transfer foil to the surface of the adherend and peeling the substrate thereafter as shown in the above method, However, the transfer foil may be adhered to the surface of the adherend, and then the active energy ray may be irradiated from the substrate side and heated as necessary to completely cure the semi-cured transfer layer , And then peeling the base material.

As the active energy ray, ultraviolet rays, X rays, radiation, ionizing radiation, ionizing radiation (alpha, beta, gamma rays, neutron beam, electron beam) can be used and light including a wavelength of 350 nm or less is preferable.

The irradiation of the active energy ray can be carried out by using a known apparatus such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer lamp, a carbon arc lamp or a xenon arc lamp, The light source is preferably a light source including light having a wavelength in the range of 150 to 350 nm and more preferably a light source having light having a wavelength in the range of 250 to 310 nm.

The amount of irradiation light irradiated to sufficiently cure the transfer layer in the semi-cured state may be, for example, about 0.1 to 100 J / cm 2, and the film curing efficiency (the relationship between irradiation energy and film curing degree) , It is preferably about 1 to 10 J / cm 2, more preferably about 1 to 5 J / cm 2.

The transfer layer formed by the transfer foil of the present invention preferably has a structure in which the carbon content of the surface portion is smaller than the carbon content of the back portion and the carbon content of the surface portion at 2 nm in the depth direction from the surface, More preferably 80% or less of the carbon content of the back surface portion in the direction 10 nm, and more preferably 2 to 60%. Here, the carbon content of the surface portion is smaller than the carbon content of the back portion means that the total carbon content from the surface to the center portion is smaller than the total carbon content from the back surface to the center portion.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (Preparation of release agent composition)

(Manufactured by Hitachi Chemical Co., Ltd., TESPINE (registered trademark) 305, solid component 50%, toluene / xylene / isobutanol / methanol mixed solution) was added to a solution of?,? - polybutadiene NISSO PB (registered trademark) G-2000, Mn = 1800 to 2200, 1,2-bond / 1,4-bond> 85/15 (molar ratio), hydroxyl value: 35 To 55 KOHmg / g) was added thereto so that the weight ratio of the solids was 85/15, and the mixture was diluted with a mixed solvent (toluene / isobutyl alcohol = 7/3) to a solid concentration of 15 wt%. Further, 7% by weight (relative to solid content) of a dryer 900 (paratoluenesulfonic acid diluent) was added as a curing agent to prepare Composition [A-1].

Example 2 (Preparation of release agent composition)

The composition [A-2] was obtained in the same manner as in Example 1, except that the solid weight ratio of the long-chain alkyl group-containing aminoalkyd resin solution to the?,? - polybutadiene diglycol was 80/20, .

Example 3 (Preparation of release agent composition)

The composition [A-3] was obtained in the same manner as in Example 1, except that the solid content weight ratio of the long-chain alkyl group-containing aminoalkyd resin solution and the?,? - polybutadiene diglycol was 75/25, Was prepared.

Example 4 (Preparation of release agent composition)

A-4] was obtained in the same manner as in Example 1, except that the solid content weight ratio of the long-chain alkyl group-containing aminoalkyd resin solution and the?,? - polybutadiene diglycol was 70/30, .

Comparative Example 1 (Preparation of release agent composition)

A composition [A-5] was prepared in the same manner as in Example 1 except that?,? - polybutadiene diglycol was not used.

Example 5 (Production of release agent-treated film)

The release agent compositions [A-1] to [A-5] were coated on a polyethylene terephthalate film (Tetoron DuPont Film Co., Ltd., Tetoron G2P2) with a thickness of 38 탆 using a bar coater to a thickness of 0.5 탆 And dried at 150 캜 for 30 seconds by a hot-air circulating dryer to obtain a release agent-treated film.

[Evaluation of release agent-treated film]

The releasing agent treatment film obtained by using the releasing agent compositions [A-1] to [A-5] with a tensile tester type tensile tester (Shimadzu Corporation, Autograph AGS-J) (10 mm x 60 mm in dimensions).

The release layer of the releasing agent-treated film obtained by using the releasing agent compositions [A-1] to [A-4] did not crack even when the elongation was elongated up to 130%, but the releasing agent obtained by using the releasing agent composition [A- The release layer of the treated film was cracked at an elongation of 100%.

Example 6 (Preparation of composition for forming transfer layer)

51.87 g of diisopropoxybisacetyl acetonate titanium (T-50, manufactured by Nippon Soda Co., Ltd., solid content in terms of titanium oxide: 16.5 mass%) was mixed with MIBK / 2-methoxypropanol (= 90/10: 100.04 g of vinyltrimethoxysilane (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) and 71.86 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 100.00 g of a solvent, KBM-503) (vinyltrimethoxysilane / 3-methacryloxypropyltrimethoxysilane = 70/30: molar ratio). Further, 34.75 g of ion-exchanged water (2-fold mol / mole of the organosilicon compound) was slowly added dropwise with stirring to prepare a hydrolysis solution [B-1].

63.15 g of a urethane acrylate oligomer (UN-952 manufactured by Negami Kogyo Co., Ltd.) as a UV curable compound, and 47.36 g of a urethane acrylate oligomer (UN-904M manufactured by Negami Kogyo Co., Ltd.) were dissolved in [B-1] . 189.45 g of an organic solvent-dispersed colloidal silica (manufactured by Nissan Chemical Industries, Ltd., MIBK-SD) was further added and stirred in the solution of [B-1]. 9.85 g of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals) was dissolved as a photopolymerization initiator, [C-1] was prepared.

(Preparation of adhesive layer solution)

The water-based acrylic resin W-123K produced by DIC was diluted with a mixed solvent (water / IPA = 80/20) to a solid concentration of 10 wt% [D-1]. Similarly, a modified polyolefin water dispersion SBN-1232J2 manufactured by Unitika Co., Ltd. was diluted to a solid concentration of 10 wt% [E-1]. The two liquids were mixed and stirred so that the solid content ratio was 50 mass% / 50 mass% = [D-1] / [E-1] to prepare an aqueous adhesive layer solution [F-1].

(Preparation of transfer foil)

A film composition solution [C-1] for transfer layer formation was formed on a release agent-treated film obtained by using the release agent compositions [A-1] to [A-4] to a thickness of 5 탆 using a bar coater, And dried in a circulating dryer at 150 DEG C for 30 seconds to obtain a semi-cured state. G-1] to [G-1] having an adhesive layer were prepared by using a bar coater to form a film having a thickness of 1 mu m thereon and drying at 150 DEG C for 30 seconds. 4] was obtained.

Using the transfer foils [G-1] to [G-4], a hard coat layer was formed on the adherend by the following method.

Transfer papers [G-1] to [G-4] were superimposed on a plastic substrate and heated and pressurized using a laminator (LAMIGUARD IC-230PRO manufactured by Intercosmos Corporation). As the adherend, a 1 mm thick acrylic sheet (Clares, manufactured by Nitto Plastic Industries Co., Ltd.) was used. Releasing agent treatment The adherend on which the film was peeled off and transferred was completed with a conveyor type condensing type high pressure mercury lamp (manufactured by Eye Graphics, lamp output 120 W / cm, lamp 1, lamp height 10 cm, conveyor speed 4 m / min) Ultraviolet rays were irradiated at a cumulative irradiation dose of 1000 mJ / cm 2 to obtain a completely cured hard coat layer (transferring transfer layer).

[Evaluation of transfer hard coat layer]

· Adhesion test

The hard coat layer on the adherend was subjected to crosscut evaluation according to JIS K 5600-5-6 (2008).

· Pencil hardness test

The hard coat layer on the adherend was subjected to pencil hardness test according to JIS K 5600-5-4 (2008).

· Scratch resistance test

Steel wool # 0000 was attached to the rubbing tester for the hard coat layer on the adherend, and the test was performed under a load of 500 g and 20 reciprocations.

In the transfer papers [G-1] to [G-4], the peelability of the foil when peeling the releasing agent-treated film from the adherend after transfer was good. In the evaluation of the transfer hard coat layer, scratches caused by steel wool were not observed in all of the adhesiveness of 100/100, pencil hardness of 5H and the like.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention.

This application is based on Japanese Patent Application No. 2011-105835 filed on May 11, 2011, the content of which is incorporated herein by reference.

Claims (6)

Wherein the hydrocarbon-based polymer having two or more hydroxyl groups is a polyolefin-based polyol, wherein the hydrocarbon polymer having two or more hydroxyl groups is a polyolefin-based polyol. The method according to claim 1,
Wherein the aminoalkyd resin is an amino alkyd resin containing a long-chain alkyl group. The method according to claim 1,
Wherein the hydrocarbon-based polymer having two or more hydroxyl groups is a polybutadiene polyol containing at least 70% of 1,2-bonds. 4. The method according to any one of claims 1 to 3,
Wherein the hydrocarbon-based polymer having two or more hydroxyl groups has a weight average molecular weight ranging from 1,500 to 2,500. A transfer foil comprising a substrate, a release layer, and a transfer layer, wherein the release layer is obtained by coating the release agent composition described in any one of claims 1 to 3 on the substrate. 6. The method of claim 5,
Wherein the transfer layer is a layer containing a) an organic silicon compound represented by the following formula (I) and / or a condensate thereof, b) an ultraviolet curable compound, and c) a silanol condensation catalyst.
[Chemical Formula 1]

(Wherein R represents an organic group in which a carbon atom is directly bonded to Si in the formula, X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and when n is 2, And when (4-n) is 2 or more, a plurality of X's may be the same or different.