JP2008280456A - Active energy beam curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy beam curable resin composition capable of forming a coated film having a tuck free surface, forming a uniform state solution, receiving less effects from the drying condition and storing condition of the coated film, and further having a good cover coating property of the coated film after curing, with a solvent-based resin solution, and enabling the peeling off of the over-coated resin coated film repeatedly. <P>SOLUTION: This active energy beam curable resin composition containing (A) a reaction product produced by the reaction of an isocyanate compound with a monomer having (meth)acryloyl group and a functional group capable of reacting with the isocyanate group, and having ≥40°C softening temperature, and (B) a film-forming resin is provided by containing a polysiloxane part in the reaction product (A) and/or the film-forming resin (B). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition capable of forming a cured film having peelability, in particular, when this composition is applied on a substrate and dried, it is not sticky even in an uncured state. A composition capable of forming a coating having a free surface, and the cured coating has good overcoating properties of a solvent-based resin solution, and active energy ray curing that allows repeated peeling of the top coating resin coating The present invention relates to a resin composition, a composition for a release material containing the resin composition, and a method for forming a release material or a laminate using the resin composition.

  It is well known that a composition mainly composed of polysiloxane is cured on the surface of various papers, synthetic films or fibers to form a film, thereby providing a peelable property to an adhesive substance. ing. Among the release materials that use polysiloxane, those that use active energy rays to cure the coating require a short curing time, and cure without heating even substrates that are damaged by thermal energy. There are advantages such as being able to make it.

  Various ultraviolet curable silicones have been developed as active energy rays for curing the coating (Japanese Patent Laid-Open Nos. 56-166224, 60-84329, and 1-311103). reference).

However, these UV curable silicone coatings are sticky in an uncured state and are inferior in handleability, so that they are not sticky even in an uncured state, that is, they are desired to be tack-free. Inappropriate.
For example, in the case where the coating formed on the substrate is embossed and then cured, it is desired that the coating is non-sticky and non-fluid so that the embossed shape is satisfactorily maintained until the curing is completed. Further, even when the laminate is temporarily wound and stored after the coating is formed, it is important that the coating is tack-free so that the coating does not adhere to the back surface of the substrate.

As a resin composition that can form a cured film having peelability and is not sticky even in an uncured state, that is, a film having a tack-free surface, an isocyanate and a (meth) acrylic compound A method of adding a silicone compound to a urethane acrylate compound having a softening temperature of 40 ° C. or higher has been proposed (Japanese Patent Laid-Open No. 2005-186516).
However, in this method, since the compatibility of the urethane acrylate compound and the silicone compound is low, when the solid content concentration is high, phase separation occurs and an opaque cloudy solution is obtained. In addition, since the silicone compound is liberated, the behavior of the silicone compound in the film is likely to change depending on the solvent drying conditions (temperature, humidity, etc.) after coating, and stable film properties may not be obtained. . In addition, the physical properties of the coating film may change depending on the storage conditions of the coating film, and as a result, the performance of overcoating the solvent-based resin solution and the number of repeated peeling of the resin coating film may be reduced.
JP-A-56-166224 JP 60-84329 A Japanese Patent Laid-Open No. 1-311103 JP 2005-186516 A

  The present invention is an active energy ray-curable resin composition capable of forming a coating having a tack-free surface even in an uncured state, in which the solution is uniform and the coating is dried. It is intended to provide an active energy ray-curable resin composition that is less affected by conditions and storage conditions, and that the cured film has good top coatability of the solvent-based resin solution and can be repeatedly peeled off from the topcoat resin film. Objective.

As a result of intensive studies, the inventors of the present invention include a specific reaction product (A) and a film-forming resin (B), and the polysiloxane moiety is a reaction product (A) and / or a film-forming resin (B). The present inventors have found that the above-described problems can be solved as long as they are included as a partial structure bonded therein.
That is, the gist of the present invention is as follows.

[1] A reaction product (A) produced by a reaction between an isocyanate compound and a monomer having a functional group capable of reacting with a (meth) acryloyl group and an isocyanate group, and having a softening temperature of 40 ° C. or higher; An active energy ray-curable resin composition containing a film-forming resin (B), characterized in that the reaction product (A) and / or the film-forming resin (B) contains a polysiloxane moiety. An active energy ray-curable resin composition.

[2] The active energy ray-curable resin composition according to [1], wherein the reaction product (A) and the film-forming resin (B) contain a polysiloxane moiety.

[3] The active energy ray-curable resin according to [1] or [2], wherein the content of the polysiloxane moiety in the active energy ray-curable resin composition is 0.5 to 50% by weight. Composition.

[4] The active energy ray-curable resin composition according to any one of [1] to [3], wherein the polysiloxane moiety has a weight average molecular weight of 500 to 15000.

[5] The active energy ray-curable resin composition according to any one of [1] to [4], wherein the polysiloxane moiety is composed of polydimethylsiloxane.

[6] The active energy ray-curable resin composition according to any one of [1] to [5], wherein the polysiloxane moiety in the film-forming resin (B) is a polymer of (meth) acryloyl group-modified polydimethylsiloxane. object.

[7] The active energy ray-curable resin composition according to any one of [1] to [6], wherein the isocyanate compound is a trimer of a diisocyanate compound.

[8] The active energy ray-curable resin composition according to any one of [1] to [7], wherein the isocyanate compound has an isocyanate group bonded to a cyclic hydrocarbon.

[9] A mold release composition comprising the active energy ray-curable resin composition according to any one of [1] to [8].

[10] The method includes a step of applying the active energy ray-curable resin composition according to any one of [1] to [8] to a substrate, and then irradiating the coating film with an active energy ray to cure. A method for forming a release material or a laminate.

  The active energy ray-curable resin composition of the present invention is non-sticky even in an uncured state, that is, can form a film having a tack-free surface, and the solution is uniform, Less affected by drying and storage conditions. Moreover, the cured film has good top coatability of the solvent-based resin solution, and can provide an excellent release material and laminate capable of repeatedly peeling the top-coated resin film.

  Hereinafter, embodiments of the present invention will be described in detail.

In the present specification, the (meth) acryloyl group means an acryloyl group and / or a methacryloyl group, the (meth) acrylic compound means an acrylic compound and / or a methacrylic compound, and (meth) acrylate and Means acrylate and / or methacrylate, and (meth) acrylic acid means acrylic acid and / or methacrylic acid.
Moreover, in this specification, a weight average molecular weight is the value of polystyrene conversion by a gel permeation chromatograph (GPC) method.

[Active energy ray-curable resin composition]
The active energy ray-curable resin composition of the present invention is produced by a reaction between an isocyanate compound and a monomer having a functional group capable of reacting with a (meth) acryloyl group and an isocyanate group. An active energy ray-curable resin composition comprising a reaction product (A) and a film-forming resin (B), wherein the reaction product (A) and / or the film-forming resin (B) It contains a polysiloxane moiety.

{Reaction product (A)}
The reaction product (A) is a monomer having an isocyanate compound and a functional group capable of reacting with a (meth) acryloyl group and an isocyanate group (hereinafter, sometimes abbreviated as “specific (meth) acrylic compound”). In addition to the isocyanate compound and the specific (meth) acrylic compound, other active hydrogen compounds that can react with the isocyanate compound may also be obtained by the reaction.

<Isocyanate compound>
The isocyanate compound used in the present invention is a compound having at least one isocyanate group, and preferably a compound having two or more isocyanate groups. For example, monoisocyanates such as phenyl isocyanate, xylyl isocyanate, naphthyl isocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, aliphatic diisocyanates such as 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4-methylenebis ( Cycloaliphatic diisocyanates such as cyclohexyl isocyanate), aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and the above diisocyanate compounds Of the above diisocyanates and active hydrogen compounds such as trimethylol group 3 of pan: 1 can be used as the reaction product of (molar ratio). Hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like can also be used.

  These isocyanate compounds may be used individually by 1 type, and may use 2 or more types together.

  As the isocyanate compound used in the present invention, in particular, a compound having an isocyanate group bonded to a non-aromatic hydrocarbon ring (cyclic hydrocarbon), a trimer of a so-called alicyclic diisocyanate compound, or a reaction with an active hydrogen compound The product is preferred. A trimer of isophorone diisocyanate and a reaction product of 3: 1 (molar ratio) of isophorone diisocyanate and trimethylolpropane are more preferable, and a trimer of isophorone diisocyanate is more preferable.

<Specific (meth) acrylic compound>
Examples of the functional group capable of reacting with the isocyanate of the specific (meth) acrylic compound include a hydroxyl group and a carboxyl group having an active hydrogen group.
In particular, a reaction product of an isocyanate compound and a specific (meth) acrylic compound having a (meth) acryloyl group and a hydroxyl group is referred to as urethane acrylate.

  As a specific (meth) acrylic compound having a hydroxyl group, a hydroxy ester which is a reaction product of (meth) acrylic acid and a polyhydroxy compound is a typical compound. Furthermore, the compound etc. which added ethylene oxide, propylene oxide, caprolactone, etc. to the hydroxyl group of this hydroxy ester are mentioned. Furthermore, the compound which esterified a part of hydroxyl group of this hydroxy ester with monocarboxylic acid is also mentioned.

  Some examples are hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate Such as hydroxy (meth) acrylate, isocyanuric acid diacrylate, pentaerythritol diacrylate monostearate, 2-hydroxy-3-phenoxypropyl acrylate, and these caprolactone adducts, ethylene oxide adducts, propylene oxide adducts, ethylene oxide Examples include propylene oxide adducts.

  Moreover, the hydroxyl group of epoxy acrylate can also be utilized. Specific examples of the compound include 2 in 1 molecule such as neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and the like. Mention may be made of epoxy acrylates obtained by reacting a compound having one epoxy with acrylic acid. Since these components have two (meth) acryloyl groups in one molecule, they also have an effect of improving the crosslinking density.

  Specific (meth) acrylic compounds having a carboxyl group include (meth) acrylic acid itself and the above hydroxy (meth) acrylate, carboxylic acid anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydro Examples include compounds obtained by reacting phthalic anhydride and the like.

  Some examples are pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipentaerythritol pentaacrylate maleic acid monoester, pentaerythritol triacrylate phthalate Acid monoester, dipentaerythritol triacrylate phthalic acid monoester, pentaerythritol triacrylate tetrahydrophthalic acid monoester, dipentaerythritol pentaacrylate tetrahydrophthalic acid monoester and the like.

  These specific (meth) acrylic compounds may be used alone or in combination of two or more.

<Other active hydrogen compounds>
In the reaction between the isocyanate compound and the specific (meth) acrylic compound, other active hydrogen compounds capable of reacting with the isocyanate compound can be used in combination. When such an active hydrogen compound is selected and used in accordance with the purpose, there is an effect of increasing the softening temperature of the resulting curable composition and an effect of increasing the flexibility of the finally obtained cured coating film. As such an active hydrogen-containing compound, a hydroxyl group-containing compound is usually used, but an amino group-containing compound or a carboxyl group-containing compound can also be used.

  Examples of the hydroxyl group-containing compound include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 2-hydroxyethyl-1,6-hexanediol, 1,2,4-butanetriol, erythritol, sorbitol, Polyhydric alcohols having three or more hydroxyl groups such as pentaerythritol and dipentaerythritol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3- Propanediol, 2-bu Lu-2-ethyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 2 -Ethyl-1,3-hexanediol, neopentyl glycol, 1,3,5-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol 1,9-nonanediol, aliphatic glycols such as 2-methyl-1,8-octanediol, alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, xylylene glycol, bis Aromatic glycols such as hydroxyethoxybenzene are used.

  High molecular weight polyols such as polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols, and polyacryl polyols can also be used.

Polyether polyols include glycols such as bisphenol A, ethylene glycol, propylene glycol and diethylene glycol, polyols having three or more hydroxyl groups such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol, or ethylenediamine and toluene. Examples include polyamines such as diamines obtained by addition polymerization of alkylene oxides such as ethylene oxide and propylene oxide, and polytetramethylene ether glycols obtained by ring-opening polymerization of tetrahydrofuran.

  Polyester polyols include dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid and phthalic acid, or carboxylic acids such as tri- and tetracarboxylic acids such as trimellitic acid and pyromellitic acid, and ethylene glycol and propylene glycol. 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2-diethylpropanediol, 2-ethyl-2-butylpropanediol, 1,6-hexanediol Diols such as neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, or aromatic polyhydroxy such as bisphenol A and bisphenol F What is obtained by polycondensation reaction with a compound is mentioned.

  Examples of the polyether ester polyol include those obtained by reacting polyester glycol with an alkylene oxide, or those obtained by reacting the above-mentioned dicarboxylic acid or anhydride thereof with an ether group-containing diol or a mixture thereof with another glycol. (Polytetramethylene ether) adipate and the like.

Polycarbonate polyol is obtained by dealcoholization condensation reaction between polyhydric alcohol and dialkyl carbonate such as dimethyl or diethyl, dephenol condensation reaction between polyhydric alcohol and diphenyl carbonate, deethylene glycol condensation reaction between polyhydric alcohol and ethylene carbonate, etc. A polycarbonate polyol is mentioned. Examples of the polyhydric alcohol used in this condensation reaction include 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5-pentane. Aliphatic diols such as diols, 2,2-diethylpropanediol, 2-ethyl-2-butylpropanediol, neopentyl glycol, or alicyclics such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol Diols can be mentioned.

  Examples of the amino group-containing compound (amine compound) include hexamethylenediamine, xylylenediamine, isophoronediamine, N, N-dimethylethylenediamine, and the like. Also, amino alcohols such as monoethanolamine and diethanolamine can be used as the active hydrogen-containing compound.

  Examples of the carboxyl group-containing compound (organic carboxylic acid) include lauric acid, stearic acid, oleic acid, palmitic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like.

  These active hydrogen compounds other than the specific (meth) acrylic compound may be used alone or in combination of two or more.

  These active hydrogen compounds other than the specific (meth) acrylic compound are specific (meth) acrylic so as not to impair the properties of the reaction product (A) obtained by the reaction between the isocyanate compound and the specific (meth) acrylic compound. The active hydrogen compound is preferably used so that the molar ratio of the reactive group of the active hydrogen compound to the reactive group of the compound is 50% or less, particularly 40% or less.

<Polysiloxane site>
The present invention is characterized by containing a polysiloxane moiety in the reaction product (A) of the isocyanate compound and the specific (meth) acrylic compound and / or the film-forming resin (B).
A polysiloxane having an active hydrogen functional group in an active hydrogen compound other than the specific (meth) acrylic compound as a method for incorporating a polysiloxane moiety into the reaction product (A) of the isocyanate compound and the specific (meth) acrylic compound It is preferable to use a compound.
Examples of the polysiloxane compound having an active hydrogen functional group include hydroxyl group-modified, amino group-modified, mercapto group-modified, and carboxyl group-modified polysiloxane compounds.

  Specific examples of the hydroxyl group-modified polysiloxane include hydroxyl group-modified polydimethylsiloxane (FM-4411 manufactured by Chisso Corporation, weight average molecular weight 1000, FM-4421: weight average molecular weight 5000, FM-4425: weight average molecular weight: 10,000, X-22-160AS manufactured by Shin-Etsu Chemical Co., Ltd .: weight average molecular weight 1000, KF6001), one-end hydroxyl group-modified polydimethylsiloxane (manufactured by Chisso Corporation FM-0411: weight average molecular weight 1000, FM-0421: weight average molecular weight 5000, FM-0425: weight average molecular weight 10,000), α-butyl-ω- [3- (2,2- (dihydroxymethyl) butoxy) propyl] polydimethylsiloxane (manufactured by Chisso Corporation FM-DA11: weight average molecular weight 1000, DA -21: weight average molecular weight 5000, DA -26: weight average molecular weight 15000) and the like.

  As the amino group-modified polysiloxane, both terminal amino group-modified polydimethylsiloxane (BY16-853 manufactured by Toray Dow Corning Silicone, X-22-161AS manufactured by Shin-Etsu Chemical Co., Ltd., FM-3311: manufactured by Chisso Corporation) 1000, FM-3321: weight average molecular weight 5000, FM-3325: weight average molecular weight 10,000), one-end amino group-modified polydimethylsiloxane (TOSHIBA Silicone Corp. TSF4700: weight average molecular weight 3000), side chain amino group-modified polydimethylsiloxane (Shin-Etsu Chemical Co., Ltd. KF-865) and the like.

  Examples of the mercapto group-modified polysiloxane include both-end mercapto group-modified polydimethylsiloxane (X-22-167B, KF-2001, manufactured by Shin-Etsu Chemical Co., Ltd.), one-end mercapto group-modified polydimethylsiloxane, and the like.

  As the carboxyl group-modified polysiloxane, both terminal carboxyl group-modified polydimethylsiloxane (X-22-167A manufactured by Shin-Etsu Chemical Co., Ltd., BY16-750 manufactured by Toray Dow Corning Silicone), one-end carboxyl group-modified polydimethylsiloxane, side chain And carboxyl group-modified polydimethylsiloxane (SF8418 manufactured by Toray Dow Corning Silicone).

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

<Reaction of isocyanate compound with specific (meth) acrylic compound / other active hydrogen compounds>
The reaction of the isocyanate compound with the specific (meth) acryl compound and other active hydrogen compounds used in combination is preferably carried out using a solvent. By using a solvent, the reaction can be easily controlled, and the viscosity of the reaction product can be adjusted.

  Examples of the solvent include inert solvents commonly used for this type of reaction, for example, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, and isobutyl acetate. Ester solvents, glycol ether ester solvents such as diethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, ether solvents such as tetrahydrofuran and dioxane, An aprotic polar solvent such as N-methylpyrrolidone is used. These may be used alone or in combination of two or more.

  In the reaction, the reaction raw material is added to the solvent so that the concentration of the reaction product in the reaction product solution is 30 to 80% by weight, and if necessary, about 0.01 to 0.1% by weight with respect to the reaction raw material. In the presence of a catalyst such as an organotin catalyst.

  The charging ratio of the isocyanate compound to the specific (meth) acrylic compound and other active hydrogen compound used in combination with the specific (meth) acrylic compound and other compounds capable of reacting with one mole of isocyanate group of the isocyanate compound. It is preferable that the functional group of the active hydrogen compound is 0.5 mol or more, particularly 1 mol or more. The upper limit of the charging ratio is preferably 3 mol or less in order to avoid a decrease in softening temperature due to the liberated specific (meth) acrylic compound and other active hydrogen compounds.

  The reaction time is usually about 3 to 15 hours, but it is preferable to monitor the content of isocyanate groups in the reaction product liquid by analysis and stop the reaction when this reaches a target value.

<Softening temperature>
The softening temperature of the reaction product (A) produced by the reaction of the polyisocyanate compound of the present invention with the specific (meth) acrylic compound and other active hydrogen compound used in combination may include the case of containing a polysiloxane moiety. And 40 ° C. or higher, preferably 50 ° C. or higher. When the softening temperature of this reaction product (A) is too low, coating film defects such as blocking of the coating film before curing may occur. The upper limit of the softening temperature of the reaction product (A) is usually about 120 ° C.

In addition, the softening temperature prescribed | regulated by this invention is the value measured on condition of the following about what remove | excluded the solvent from the reaction product (A).
Equipment used: TMA6100 manufactured by Seiko Instruments Inc.
Measurement mode: TMA penetration mode Measurement temperature range: 30 to 230 ° C., temperature increase rate: 5 ° C./minute penetration cross-sectional area: 0.758 mm ² (1 mmφ), load: 50 g
The penetration start temperature when measured under the above conditions is the softening temperature.

{Film-forming resin (B)}
The film-forming resin (B) in the present invention is not particularly limited as long as it has an appropriate film-forming property, and is preferably a (meth) acrylic resin, an acrylic styrene resin, an epoxy resin, a polyurethane resin, Polyester resin, polyvinyl alcohol, polyvinyl acetal, and the like can be used.

When the polysiloxane part is contained in the film-forming resin, it is more preferable because the compatibility with the reaction product (A) containing the polysiloxane part and the number of repeated peeling of the resin overcoat film are improved.
The polydimethylsiloxane moiety in the film-forming resin (B) may exist in the form of a graft copolymer or may exist in the form of a block copolymer.
Of the film-forming resins described above, a (meth) acrylic resin is particularly preferable from the viewpoint of adhesion to a substrate and film-forming properties.

  For example, a (meth) acrylic resin containing a polysiloxane moiety can be obtained by copolymerization of a (meth) acryloyl group-modified polysiloxane and a vinyl monomer.

  As a specific compound of (meth) acryloyl group-modified polysiloxane, one-end acryloyl group-modified polydimethylsiloxane (FM-0771 manufactured by Chisso Corporation, weight average molecular weight 1000, FM-0721: weight average molecular weight 5000, FM-0725: weight Average molecular weight 10,000), acryloyl group-modified polydimethylsiloxane (Shin-Etsu Chemical Co., Ltd. X-22-164B, X-22-164C: weight average molecular weight 5000), and the like. One-terminal (meth) acryloyl group-modified polydimethylsiloxane is preferred.

Examples of vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, Aliphatic or cyclic (meth) acrylate such as isobornyl (meth) acrylate, tricyclodecyl (meth) acrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-buty Vinyl ethers such as vinyl ether and isobutyl vinyl ether, styrenes such as styrene and α-methylstyrene, nitrile monomers such as acrylonitrile and methacrylonitrile, fatty acid vinyl such as vinyl acetate and vinyl propionate, vinyl chloride, vinylidene chloride, Halogen-containing monomers such as vinyl fluoride and vinylidene fluoride, olefins such as ethylene, propylene and isoprene, dienes such as chloroprene and butadiene, and epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate and glycidyl allyl ether Maleic anhydride, methacrylic acid, maleimide group-containing methacrylate, and the like.
Among these, a copolymer containing an aliphatic cyclic (meth) acrylate such as isobornyl (meth) acrylate or tricyclodecyl (meth) acrylate is effective for improving the number of repeated peeling and is particularly preferable.

  The (meth) acryloyl group-modified polysiloxane and the vinyl monomer are used alone or in appropriate mixture.

  The proportion of each monomer in the (meth) acrylic resin containing a polysiloxane moiety is preferably 1 to 80% by weight of (meth) acryloyl group-modified polysiloxane, 20 to 99% by weight of vinyl monomer, more preferably ( It is 5 to 50% by weight of polysiloxane modified with methacryloyl group and 50 to 95% by weight of vinyl monomer.

  In addition, an acrylic styrene resin, polyvinyl alcohol, and polyvinyl acetal containing a polysiloxane moiety can be obtained by copolymerization of the vinyl monomer with a vinyl group-modified polysiloxane and / or a (meth) acryloyl group-modified polysiloxane. . Moreover, the epoxy resin, polyurethane resin, and polyester resin having a polysiloxane moiety are respectively the reaction of the epoxy group, isocyanate group, and carboxyl group that the epoxy resin, polyurethane resin, and polyester resin have with an active hydrogen group polysiloxane. Can be obtained.

  In addition, illustration of the said film forming resin (B) does not limit this invention. These film-forming resins (B) may be used alone or in combination of two or more.

  From the viewpoint of tack-free, the glass transition temperature (Tg) of the film-forming resin (B) is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. The upper limit of the glass transition temperature (Tg) of the film-forming resin (B) is usually 200 ° C. or lower.

  The weight average molecular weight of the film-forming resin (B) is not particularly limited, but is preferably 10,000 to 500,000, particularly preferably 30,000 to 200,000. If the molecular weight is larger than this range, the compatibility with the reaction product (A) is not sufficient, and if it is smaller, the effect of improving the softening temperature is not sufficient.

{Reaction product (A) / film-forming resin (B) mixing ratio}
The mixing ratio of the reaction product (A) and the film-forming resin (B) is usually from 95 to 5 to 5 to 95, preferably from 90 to 10, as a solid weight ratio in the active energy ray-curable resin composition. 10 to 90, more preferably 80 to 20 to 20 to 80. When there are too few reaction products (A) than this range, the heat resistance after hardening will become inadequate. In addition, by blending an appropriate amount of a resin having a film-forming property, the effect of improving the softening temperature, the adhesion to the substrate, the film-forming property, etc. can be obtained, but the film-forming resin ( If the amount of B) is too small, this effect cannot be obtained sufficiently.

{Polysiloxane moiety content / weight average molecular weight}
The content of the polysiloxane moiety in the reaction product (A) and / or the film-forming resin (B) is 0.5 to 50 as the solid content weight ratio of the polysiloxane moiety in the active energy ray-curable resin composition. % By weight, preferably 1 to 40% by weight, more preferably 5 to 30% by weight. If there are too many polysiloxane sites than this range, the coating film will be sticky, the cost will increase, and the top coatability of the solvent-based resin will be impaired. Moreover, when there are too few polysiloxane parts, the effect of peelability is not enough.

  The weight average molecular weight of the polysiloxane moiety is preferably 15000 or less, more preferably 8000 or less, still more preferably 2000 or less, preferably 500 or more, more preferably 800 or more. When the weight average molecular weight of the polysiloxane moiety is too large, the top coatability of the solvent-based resin solution tends to be lowered, and when it is too small, the peelability effect is not sufficient.

  The polysiloxane moiety according to the present invention is preferably derived from dialkylpolysiloxane and / or diarylpolysiloxane, particularly dimethylpolysiloxane, from the viewpoint of peelability.

{Other ingredients}
The active energy ray-curable resin composition of the present invention includes a reactive monomer, a reactive oligomer, a photopolymerization initiator, and a photosensitizer in addition to the reaction product (A) and the film-forming resin (B) described above. , Colorants such as pigments and dyes, inorganic fillers such as calcium carbonate, silica and mica, metal fillers such as iron and lead, other lubricants, plasticizers, antioxidants, antistatic agents, light stabilizers, UV absorbers Well-known additives such as flame retardants, flame retardant aids, polymerization inhibitors, fillers, silane coupling agents, and the like can be appropriately contained depending on the application.

  Examples of reactive monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene; vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N- Vinyl ester monomers such as vinyl-2-pyrrolidone, N-vinylcaprolactam and divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether and allyl glycidyl ether; acrylamide N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, Nt- Acrylamides such as butylacrylamide, acryloylmorpholine, methylenebisacrylamide; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, I-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth ) Tetrahydrofurfuryl acrylate, morpholyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate , Dimethylamino (meth) acrylate Chill, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, Mono (meth) acrylate such as allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, di (meth) ) Diethylene glycol acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (n = 5-14), propylene glycol di (meth) acrylate, Di (meth) acrylic acid Propylene glycol, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate (n = 5 to 14), 1,3-butylene di (meth) acrylate Glycol, 1,4-butanediol di (meth) acrylate, polybutylene glycol di (meth) acrylate (n = 3 to 16), poly (1-methylbutylene glycol) di (meth) acrylate (n = 5) -20), 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) hydroxypivalate Acrylic acid ester, di (meth) acrylate of dicyclopentanediol, trimer Tyrolpropane tri (meth) acrylate, pentaesitol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, trimethylolpropane polyoxy Propyl (meth) acrylate, Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, Tris (2-H Roxyethyl) isocyanurate di (meth) acrylate, ethylene oxide added bisphenol A di (meth) acrylate, ethylene oxide added bisphenol F di (meth) acrylate, propylene oxide added bisphenol A di (meth) acrylate, propylene oxide added bisphenol F di ( And polyfunctional acrylates such as meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, and bisphenol F epoxy di (meth) acrylate. These may be used alone or in combination of two or more.

  As the reactive oligomer, it is preferable to use epoxy acrylate, polyester acrylate, polyether acrylate, or the like. These may be used alone or in combination of two or more.

  Examples of the photopolymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, Thioxanthones such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one (for example, manufactured by Ciba Specialty Chemicals) Darocur 1173), benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone (eg Irgacure 184 from Ciba Specialty Chemicals), 2-methyl-2-morpholine Acetophenones such as (4-thiomethylphenyl) propan-1-one (for example, Irgacure 907 manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoin methyl Benzoin ethers such as ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine Oxides, acylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate (for example, a product manufactured by Stofer Co., Ltd.) Interview A 55), 1,7-bis acridinyl heptane, 9-phenyl acridine, and the like. Of these, acetophenone type photopolymerization initiators are preferred. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

  In addition, the reactive monomer and the reactive oligomer are radical polymerizable compounds, and when a compound having a radical polymerizable group and a cationic polymerizable group such as an epoxy group is used as the radical polymerizable compound, the above light is used. A photocationic polymerization initiator may be used in combination with the radical polymerization initiator, and the type of the photocationic polymerization initiator in that case is not particularly limited, and conventionally known ones can be used.

  The addition amount of a photoinitiator is 0.1 to 10 weight% with respect to solid content of an active energy ray resin composition, More preferably, it is 0.5 to 7 weight%, More preferably, it is 1 to 5 weight%. . If the addition amount of the photopolymerization initiator is too small, the photocurability is extremely lowered depending on the type of active energy ray, which is substantially unsuitable for industrial production. On the other hand, if the amount is too large, odor may remain in the cured film when the amount of irradiation light is small.

  In addition, when using an electron beam as an active energy ray, it is usually preferable not to add the photopolymerization initiator. Moreover, when using infrared rays, visible rays, or ultraviolet rays, it is usually preferable to add the photopolymerization initiator.

  A known photosensitizer can be added to the active energy ray-curable resin composition according to the present invention as necessary. Examples of the photosensitizer include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethyl. Examples include aminoacetophenone. These photosensitizers may also be used alone or in combination of two or more.

  The viscosity of the active energy ray-curable resin composition according to the present invention can be adjusted according to the application and use mode. Generally, when measured using a rotary E-type viscometer, The viscosity is preferably about 5 to 10,000 mPa · s from the viewpoints of handleability, coatability, moldability, and three-dimensional formability, and more preferably about 10 to 5000 mPa · s. Particularly preferred is 10 to 1000 mPa · s. The adjustment of the viscosity of the active energy ray-curable resin composition should be performed by adjusting the blending ratio of the reaction product (A), the film-forming resin (B), and other additive components, or by dilution with a solvent exemplified below. Can do.

Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate, diethylene glycol ethyl ether acetate, propylene Glycol ether ether solvents such as glycol methyl ether acetate, propylene glycol monomethyl ether, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, ether solvents such as tetrahydrofuran and dioxane, N-methylpyrrolidone, etc. These aprotic polar solvents are used. These may be used alone or in combination of two or more.
In view of the solubility and solvent volatility of the active energy resin composition, the solvent is preferably methyl ethyl ketone or ethyl acetate.

  In the active energy ray-curable resin composition of the present invention, the softening temperature in an uncured state excluding the solvent is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. When the softening temperature is too low, the coating film is sticky and a tack-free surface cannot be obtained. In order to set the softening temperature of the active energy ray-curable resin composition to such a softening temperature, the contents of the reaction product (A), the film-forming resin (B), and other components may be appropriately adjusted. . In addition, it can measure similarly to the softening temperature of the above-mentioned reaction product (A) also about the softening temperature of an active energy ray curable resin composition.

[Method for Forming Release Material Composition / Release Material or Laminate]
The above-mentioned active energy ray-curable resin composition of the present invention is mainly used for coating applications, forming an embossable film, protecting an underlayer and / or a substrate, forming a laminate, preferably a release material. Used for formation.

Examples of the substrate on which the active energy ray-curable resin composition of the present invention is applied include paper, wood, cloth, rubber, polyethylene, polypropylene, polyester, vinyl chloride, polyurethane, acrylic, polycarbonate, ABS, polyamide, nylon, epoxy Resins, plastics such as phenol resin and melamine resin, metals and alloys such as iron, stainless steel, aluminum, tin, tin, and galvanized steel, and inorganic substances such as glass, ceramic, brick, and concrete can be used.
There is no restriction | limiting in particular in the shape of a base material, A molded object of a film, a sheet | seat, and various shapes can be used. The base material may be appropriately provided with a sealing layer, a primer layer, coating, or the like.

  The coating method of the active energy ray-curable resin composition of the present invention on the base material includes bar coater method, applicator method, curtain flow coater method, roll coater method, spray method, gravure coater method, comma coater method, reverse A known method such as a roll coater method, a lip coater method, a die coater method, a slot die coater method, an air knife coater method, a dip coater method, or coating with a roller or a brush is used.

  After coating, the solvent is evaporated to form a coating film. Although the thickness of a coating film is set according to a use and there is no restriction | limiting in particular, it is 0.1-300 micrometers normally in the dry film thickness after solvent evaporation, Preferably it is 0.5-150 micrometers.

  In addition, as the active energy ray used when curing the coating film of this active energy ray-curable resin composition to produce a release material or a laminate, infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays, etc. can be used. It is preferable to use an electron beam or an ultraviolet ray from the viewpoint of apparatus cost and productivity. As a light source, an electron beam irradiation apparatus, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, Ar Lasers, He—Cd lasers, solid lasers, xenon lamps, high frequency induction mercury lamps, sunlight, and the like are suitable. As the ultraviolet light source, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, or the like is used.

The irradiation amount of the active energy ray varies depending on the active energy ray to be used. For example, in the case of curing by electron beam irradiation, the irradiation amount is preferably 1 to 10 Mrad. Moreover, in the case of ultraviolet irradiation, it is preferable that the irradiation amount is 50-1500 mJ / cm < ² >.

  The atmosphere during curing may be any of an inert gas such as air, nitrogen, or argon, or a sealed space between a film, glass, or the like and a metal mold.

  EXAMPLES Next, although an Example demonstrates this invention more specifically, this invention is not limited to a following example, unless the summary is exceeded. In addition, solid content as described in the following Examples and Comparative Examples refers to components excluding the solvent component.

Synthesis of urethane acrylate (I);
A reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 48.6 g of methyl ethyl ketone and 48.6 g of isophorone diisocyanate trimer (manufactured by Degussa, VESTANAT T1890), and the temperature was raised to 60 ° C. And dissolved. Dioctyltin dilaurate 0.16g and ethylene glycol 0.62g were added here, and it was made to react at 60 degreeC for 2 hours. Subsequently, 40.0 g of one-terminal hydroxyl group-modified polydimethylsiloxane (FM-0411 manufactured by Chisso Corporation: weight average molecular weight 1000) was added and reacted at 60 ° C. for 2 hours. Next, 0.09 g of hydroquinone monomethyl ether and 58.6 g of pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Biscoat 300) were charged and reacted at 60 ° C. for 5 hours. The reaction product solution was analyzed by infrared absorption spectrum, and it was confirmed that the absorption of the isocyanate group had disappeared. Then, 147.8 g of methyl ethyl ketone was added to complete the reaction. As a result, urethane acrylate (I) containing a polysiloxane moiety in the structure was obtained. The softening temperature of the coating film coated with this reaction product and dried from methyl ethyl ketone was 56 ° C.

Synthesis of urethane acrylate (b);
The charge weight of each raw material was changed to the amount shown in Table 1, and urethane acrylate (B) containing a polydimethylsiloxane moiety in the structure was synthesized according to the method shown in the synthesis of urethane acrylate (I). The softening temperature of the coating film obtained by applying this reaction product liquid and evaporating and drying methyl ethyl ketone was 62 ° C.

Synthesis of urethane acrylate (C);
A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was charged with 48.6 g of methyl ethyl ketone and 242.8 g of a trimer of isophorone diisocyanate (manufactured by Degussa, VESTANAT T1890), and the temperature was raised to 60 ° C. And dissolved. Here, dioctyltin dilaurate 0.18 g, 1,4-butanediol 13.5 g, 2-hydroxyethyl acrylate 46.4 g, hydroquinone monomethyl ether 0.09 g, and pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Biscoat) 300) 146.6 g was charged and reacted at 60 ° C. for 5 hours. The reaction product solution was analyzed by infrared absorption spectrum, and after confirming that the absorption of the isocyanate group had disappeared, 147.8 g of methyl ethyl ketone was added to terminate the reaction. As a result, urethane acrylate (C) was obtained. The softening temperature of the coating film obtained by applying this reaction product liquid and drying methyl ethyl ketone was 58 ° C.

  Table 1 below summarizes the raw material compositions of urethane acrylates (A) to (C), the polysiloxane moiety content, and the softening temperature.

Synthesis of film-forming resin (a);
A reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 72 g of methyl methacrylate, 18 g of acryloyl group-modified polydimethylsiloxane (manufactured by Chisso Corporation, FM-0711, weight average molecular weight 1000) and 180 g of methyl ethyl ketone, The mixture was heated to the reflux temperature of methyl ethyl ketone (about 83 ° C.). Furthermore, 0.09 g of dimethyl-2,2-azobis (2-methylpropionate) (manufactured by Wako Pure Chemicals, V-601) was added and reacted for 3 hours, and then 0.27 g was added 5 times every 3 hours. And polymerized. Thereafter, 30 g of methyl ethyl ketone was added to complete the reaction. The obtained film-forming resin (a) had a polystyrene equivalent weight average molecular weight of 79000 and a glass transition temperature (Tg) of 89 ° C.

Synthesis of film-forming resins (b) to (e);
The charge weight of each raw material was changed to the amount shown in Table 2, and the film forming resins (b) to (e) were respectively synthesized according to the method shown in the synthesis of the film forming resin (a).

  Table 2 below summarizes the raw material charge weight, weight average molecular weight, and glass transition temperature (Tg) of the film-forming resins (a) to (e).

Obtaining a film-forming resin (f);
A commercially available acrylic resin (Kuraray Polymethylmethacrylate Parapet GF) was used.

Synthesis of silicone compound (α);
To a reactor equipped with a stirrer, reflux condenser, dropping funnel and thermometer, methyl ethyl ketone 23. 3 g and 10 g of isophorone diisocyanate, 20.4 g of a mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate, 0.10 g of dioctyltin dilaurate, and 0.10 g of hydroquinone monomethyl ether were added, and air was blown into the solution. After the time reaction, 240.8 g of alcohol-modified silicone (FMDA21 manufactured by Chisso Corporation, weight average molecular weight 5000) was added to the reaction product obtained by reacting for 5 hours while intermittently raising the temperature to 80 ° C., and further 5 hours. After the reaction, 609.3 g of methyl ethyl ketone was added and cooled to obtain a silicone compound (α). When methyl ethyl ketone was distilled off from the reaction product liquid, it was a viscous liquid and the softening temperature was 40 ° C. or less, which was not measurable.

Procurement of silicone compound (β);
A commercially available hydroxyl group-terminated dimethyl silicone (manufactured by Chisso Corporation, FM-0421, weight average molecular weight 5000) was used as it was.

[Examples 1 to 7, Comparative Examples 1 and 2]
<Preparation of active energy ray-curable resin composition solution>
33 parts by weight of the above urethane acrylate (ii) and 67 parts by weight of the resin (a) having a film-forming property (all the above parts by weight are solid parts by weight) were mixed. 3 parts by weight of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 907) per 100 parts by weight of the solid content of the composition, methyl ethyl ketone as a diluent solvent at a solid content concentration of 40% by weight, and the viscosity shown in Table 3 Thus, the active energy curable resin composition solution of Example 1 was prepared.
Similarly, urethane acrylates (A), (B), (C), film-forming resins (a) to (f), silicone compounds (α), (β) are shown in Table 3 in proportions (values are either Also, the active energy curable resin compositions of Examples 2 to 7 and Comparative Examples 1 and 2 were prepared in the same manner as described above.
Table 3 shows the polysiloxane moiety content, softening temperature, and viscosity of the obtained active energy ray-curable resin composition.

The coating agent composition solution (active energy ray-curable resin composition) obtained above is applied to the paper coated with the filler with a bar coater so that the coating thickness becomes 10 μm after drying. And dried by heating at 110 ° C. for 1 minute. Next, using a high-pressure mercury lamp with an output of 120 W / cm, ultraviolet irradiation at 800 mJ / cm ² was performed to cure the coating film.

  Each coating agent composition solution and the formed cured film were evaluated as follows, and the results are shown in Table 3.

<Solution uniformity test>
The light transmittance (% T) at a wavelength of 550 nm of the coating agent composition solution prepared above was measured.
Measuring instrument: Hitachi Spectrophotometer U-1000 (optical path length: 1 cm)

<Top coatability test of resin solution>
A solvent-based resin solution blended in the following ratio in the cured film was applied with a bar coater so that the thickness of the coating film became 10 μm after drying, and heated and dried at 110 ° C. for 1 minute. At the time of coating, the polyurethane resin solution was not repelled, and it was examined whether or not the polyurethane resin coating was uniformly applied.
(Solvent resin solution)
Polyurethane resin solution (Dainippon Ink Co., Ltd., CRISVON 6116SL)
100 parts by weight Carbon black (Mitsubishi Chemical Corporation) 1 part by weight Solvent (methyl ethyl ketone) 100 parts by weight Solvent (dimethylformamide) 100 parts by weight (determination criteria)
Can be applied evenly over the entire coated surface: ○
Repels appear in the bar coater streaks:
Repels are visible on the entire surface: ×

<Repeated peel test>
Following the polyurethane resin coating applied on the above cured film, a two-component urethane adhesive having the following composition was applied with a bar coater so that the coating amount after drying was 20 g / m ² , After bonding the back skin, the adhesive was heat-cured at 120 ° C. for 2 minutes and further aged at 50 ° C. for 24 hours to form a polyurethane resin laminate. The formed polyurethane resin laminate was peeled at an angle of 90 degrees. Formation and peeling of the laminate was repeated, and the number of repeatable peels was evaluated.
(2-pack urethane adhesive)
Main agent (Dainippon Ink, CRISVON, 4070) 100 parts by weight Curing agent (Dainippon Ink, CRISVON, NX) 50 parts by weight Accelerator (Dainippon Ink, CRISVON, ACCEL, HM) 3 parts by weight Solvent (Toluene) 80 parts by weight Solvent (ethyl acetate) 40 parts by weight

<Pressurized storage stability test>
The coating composition solution is applied to a paper coated with a sealing agent, heated and dried at 110 ° C. for 1 minute, sandwiched between copy papers, and a pressure of 20 kg / cm ² (about 2 MPa) with a press. Was stored under pressure for 16 hours. After pressure storage, curing by ultraviolet irradiation was performed. The cured film was subjected to the above repeated peel test, compared with the number of peels when not stored under pressure, and evaluated according to the following criteria.
(Criteria)
Decrease in the number of peelings is 1 or less: ○
Can not be peeled off, or the number of times decreases more than twice: ×

From Table 3, the following is clear.
(1) In Examples 1 to 7, the uniformity of the coating agent composition solution, the top coatability, and the number of repeated peelings are good.
(2) In Examples 3, 4, and 6, even when pressure storage is performed in an uncured state, the number of repeated peeling is good.
From the above results, the superiority of the present invention was confirmed.

Claims (10)

  A reaction product (A) produced by a reaction of an isocyanate compound with a monomer having a functional group capable of reacting with a (meth) acryloyl group and an isocyanate group; An active energy ray-curable resin composition containing (B), wherein the reaction product (A) and / or the film-forming resin (B) contains a polysiloxane moiety. A linear curable resin composition.   The active energy ray-curable resin composition according to claim 1, wherein the reaction product (A) and the film-forming resin (B) contain a polysiloxane moiety.   The active energy ray-curable resin composition according to claim 1 or 2, wherein the content of the polysiloxane moiety in the active energy ray-curable resin composition is 0.5 to 50% by weight.   The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the polysiloxane moiety has a weight average molecular weight of 500 to 15000.   The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the polysiloxane moiety is composed of polydimethylsiloxane.   The active energy ray-curable resin composition according to any one of claims 1 to 5, wherein the polysiloxane moiety in the film-forming resin (B) is a polymer of (meth) acryloyl group-modified polydimethylsiloxane.   The active energy ray-curable resin composition according to any one of claims 1 to 6, wherein the isocyanate compound is a trimer of a diisocyanate compound.   The active energy ray-curable resin composition according to any one of claims 1 to 7, wherein the isocyanate compound has an isocyanate group bonded to a cyclic hydrocarbon.   The composition for mold release materials containing the active energy ray curable resin composition in any one of Claim 1 to 8.   A release material comprising a step of applying the active energy ray-curable resin composition according to any one of claims 1 to 8 to a base material and then irradiating the coating film with an active energy ray to cure the coating material. A method for forming a laminate.