WO2021157270A1 - Ultraviolet curable resin composition for transfer paper protective layer - Google Patents

Abstract

The present invention provides: an ultraviolet curable resin composition that is for a transfer paper protective layer and that can form a protective layer having excellent firing properties when producing transfer paper for decoration; a layered product having a protective layer having excellent firing properties; and transfer paper for decoration.　The ultraviolet curable resin composition for a transfer paper protective layer according to the present invention contains an acrylic polymer and a polymerizable compound. The acrylic polymer contains a monomeric unit derived from an alkyl(meth)acrylate having a branched alkyl group. The acrylic polymer has a mass-average molecular weight of 20,000-450,000. The polymerizable compound has, in the molecule, one or more polymerizable double bonds. The layered product and transfer paper for decoration according to the present invention are each obtained by sequentially layering: base paper; a water-soluble sizing agent layer; a printing ink layer; and a protective layer of a cured product of the ultraviolet curable resin composition for an transfer paper protective layer according to the present invention.

Description

[Name of invention determined by ISA based on Rule 37.2.] UV curable resin composition for transfer paper protective layer

The present invention relates to a resin composition for an ultraviolet curable transfer paper protective layer, a laminate, and a transfer paper for painting.
The present application claims priority based on Japanese Patent Application No. 2020-020157 filed in Japan on February 7, 2020, the contents of which are incorporated herein by reference.

There are several ways to paint on earthenware. For example, a method using transfer paper is known. In this case, the transfer paper is obtained by printing a printing ink layer containing a coloring pigment for earthenware on a mount dried by applying a water-soluble paste such as a dextrin solution, and printing a protective layer on the printing ink layer. In this method, the integrated protective layer and printing ink layer are peeled off from the mount in water, the printing ink layer is brought into contact with ceramics and dried, and then the protective layer and printing ink layer are fired at a high temperature. It is a method of painting.

Currently, an organic solvent type resin such as an organic solvent type polymethacrylic acid ester resin is mainly used for the protective layer.

However, the protective layer using the organic solvent type resin has the following problems.
(1) Since a high boiling point organic solvent is used to prevent clogging of the screen printing plate, the drying speed is slow and the productivity is low.
(2) There is a risk of causing environmental pollution due to organic solvents.
(3) Since the organic solvent dries slowly, blocking between the transfer papers by the residual solvent is likely to occur when the transfer papers are stacked.
(4) The transfer paper is liable to change with time, and the flexibility may be lost during storage to reduce the sticking suitability.

Patent Document 1 describes an acrylic polymer (A), a solvent (B), and a plasticizer (D) containing 50% by mass or more of a monomer unit derived from an alkyl (meth) acrylate having 3 to 12 carbon atoms in an alkyl group. ), A resin composition for a transfer paper protective layer is described.

Patent Document 2 describes a polymer of a compound represented by a specific general formula (A), a photopolymerizable compound represented by a specific general formula (B), and polymerization in a molecule other than the general formula (B). A resin composition for a transfer paper protective layer comprising one or more of a photopolymerizable compound having a sex double bond, a photoinitiator, and a specific non-ionic activator is described.

International Publication No. 2018/135579 Japanese Unexamined Patent Publication No. 63-126996

The resin composition for the transfer paper protective layer described in Patent Document 1 does not consider ultraviolet curing. Therefore, when ultraviolet curing is used as a curing means for the composition, it is unclear whether or not it can be applied.
Further, since the resin composition for the transfer paper protective layer described in Patent Document 1 contains an organic solvent, it may cause environmental pollution. Further, since it takes a long time to evaporate the organic solvent after printing the resin composition for the transfer paper protective layer on the printing ink layer, there is room for improvement in productivity.

In addition, in the transfer paper for painting obtained by using the resin composition for the transfer paper protective layer described in Patent Document 2, pinholes are likely to occur in the protective layer after firing, and the calcinability is insufficient.

The present invention relates to a resin composition for an ultraviolet curable transfer paper protective layer capable of forming a protective layer having excellent calcinability during the production of a transfer paper for painting, a laminate having a protective layer having excellent calcinability, and painting. Transfer paper for use is provided.

[1] The acrylic polymer contains an acrylic polymer and a polymerizable compound, and the acrylic polymer contains a monomer unit derived from an alkyl (meth) acrylate having a branched alkyl group, and the acrylic polymer contains a monomer unit. The mass average molecular weight of the above is 20000 to 450,000, and the polymerizable compound is a resin composition for an ultraviolet curable transfer paper protective layer having one or more polymerizable double bonds in the molecule.
[2] The resin composition for an ultraviolet curable transfer paper protective layer according to [1], wherein the acrylic polymer has a mass average molecular weight of 20,000 to 100,000.
[3] The content ratio of the monomer unit derived from the alkyl (meth) acrylate having a branched alkyl group is 5 to 100% with respect to 100% by mass of all the monomer units of the acrylic polymer. The resin composition for an ultraviolet curable transfer paper protective layer according to [1] or [2].
[4] The monomer unit derived from the alkyl (meth) acrylate having a branched alkyl group is a monomer unit derived from isobutyl (meth) acrylate and a single amount derived from sec-butyl (meth) acrylate. The UV-curable transfer paper protective layer according to any one of [1] to [3], which comprises at least one selected from the group consisting of a body unit and a monomer unit derived from 2-ethylhexyl methacrylate. Resin composition for.
[5] The resin composition for an ultraviolet curable transfer paper protective layer according to any one of [1] to [4], wherein the polymerizable compound contains a monofunctional monomer and a polyfunctional monomer.
[6] The polyfunctional monomer is at least one selected from the group consisting of aliphatic urethane (meth) acrylate, aromatic urethane (meth) acrylate, polyester (meth) acrylate and epoxy (meth) acrylate. The resin composition for an ultraviolet curable transfer paper protective layer according to [5].
[7] The content ratio of the monofunctional monomer is 5.0 to 65.0% by mass with respect to 100% by mass of the resin composition for the UV curable transfer paper protective layer [5] or [6]. The resin composition for an ultraviolet curable transfer paper protective layer according to.
[8] Protection comprising a mount, a water-soluble paste layer, a printing ink layer, and a cured product of the resin composition for an ultraviolet curable transfer paper protective layer according to any one of [1] to [7]. A laminated body in which layers are laminated in this order.
[9] A transfer paper for painting, which comprises the laminate according to [8].

The present invention relates to a resin composition for an ultraviolet curable transfer paper protective layer capable of forming a protective layer having excellent calcinability during the production of a transfer paper for painting, a laminate having a protective layer having excellent calcinability, and painting. Transfer paper can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of a transfer paper for painting.

"(Meta) acrylate" is a general term for acrylate and methacrylate.
"(Meta) acrylic acid" is a general term for acrylic acid and methacrylic acid.
The “monomer unit” means a structural unit formed from one monomer molecule in a polymer.
The numerical range expressed using "-" includes the numerical values on both sides of "-". In addition, the numerical range disclosed in the present specification may be an arbitrary numerical range by arbitrarily combining the lower limit value and the upper limit value.

The mass average molecular weight of the polymer is a polystyrene-equivalent value measured by the GPC-LS method (Gel Permeation Chromatography-Light Scattering Method: GPC-light scattering method).
"Mw" means mass average molecular weight.

The glass transition temperature of the polymer can be obtained from the Fox formula of the following formula from the type and mass fraction of the monomer unit.
1 / Tg = Σ ( _Wi / Tg _i )
During the ceremony
Tg is the glass transition temperature (unit: K) of the polymer.
_Wi is a mass fraction of the monomer unit i derived from the monomer i constituting the polymer.
Tg _i is the glass transition temperature (unit: K) of the homopolymer of the monomer i.
As _{the value of Tg i,} the value described in POLYMER HANDBOOK Volume 1 (WILEY-INTERSCIENCE) can be used.

The viscosity is a value measured at 25 ° C. and a rotation speed of 60 rpm using a B-type viscometer.

Isobutyl methacrylate may be referred to as "IBMA".
n-Butyl methacrylate may be referred to as "BMA".
2-Ethylhexyl methacrylate may be referred to as "EHMA".
Methyl methacrylate may be referred to as "MMA".

[Resin composition for UV curable transfer paper protective layer]
The UV-curable transfer paper protective layer resin composition (hereinafter, may be simply referred to as “resin composition”) is polymerizable with an acrylic polymer (hereinafter, may be referred to as “polymer A”). It includes a compound (hereinafter, may be referred to as “compound B”).
The resin composition comprises a radical initiator (hereinafter, may be referred to as “initiator C”), a defoaming agent (hereinafter, may be referred to as “defoaming agent D”), and a polymer, if necessary. It may further contain one or more selected from the group consisting of components other than A, compound B, initiator C and defoamer D (hereinafter, may be referred to as "other component E").

<Polymer A>
The polymer A may be a monomer unit derived from an alkyl (meth) acrylate having a branched alkyl group (hereinafter, may be referred to as “monomer a”) (hereinafter, may be referred to as “unit a”). .)including. The Mw of the polymer A is 20000 to 450,000. Since the polymer A contains the unit a, a protective layer having excellent calcinability can be formed by the resin composition.

Specific examples of the monomer a include isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. The monomer a is not limited to these.
The monomer a is at least selected from the group consisting of isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. One is preferable, and at least one selected from the group consisting of isobutyl (meth) acrylate, sec-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is more preferable from the viewpoint of calcinability of the protective layer.
The monomer a is not limited to one type, and may be two or more types. Further, the unit a is not limited to one type, and may be two or more types.

The polymer A may contain a monomer unit other than the unit a (hereinafter, may be referred to as “another monomer unit”).
The other monomer unit is a monomer derived from a monomer that can be additive-polymerized with the monomer a (hereinafter, may be referred to as “another monomer”), excluding the monomer a. If it is a unit, it is not particularly limited.
Specific examples of the other monomers are listed below, but the other monomers are not limited thereto.
Alkyl (meth) acrylate: Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Acrylate.
Monovinyl monomer: vinyl acetate, vinyl propionate, (meth) acrylonitrile.
α, β-monoethylene unsaturated carboxylic acid: (meth) acrylic acid, maleic acid, itaconic acid, crotonic acid.
Hydroxyalkyl (meth) acrylate: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate.
Amino group-containing alkyl (meth) acrylate: diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate.
Aromatic monovinyl monomer: styrene, α-methylstyrene.

Examples of the other monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl. At least one selected from the group consisting of (meth) acrylate, styrene and α-methylstyrene is preferable, and from the viewpoint of the tensile strength of the protective layer, n-butyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth). ) At least one selected from the group consisting of acrylate and styrene is more preferable, and at least one selected from the group consisting of n-butyl (meth) acrylate and styrene is even more preferable.
The other monomer is not limited to one type, and may be two or more types.

The polymer A may have a polymerizable double bond. The content ratio of the unit a in the polymer A is preferably 5% by mass or more, more preferably 20% by mass or more, still more preferably 50% by mass or more, based on the total mass of the monomer units constituting the polymer A. The content ratio of the unit a in the polymer A is 100% by mass or less of the total mass of the monomer units constituting the polymer A.
The higher the content ratio of the unit a in the polymer A, the more excellent the calcinability of the protective layer obtained by curing the resin composition.

The Mw of the polymer A is 20000 to 450,000, preferably 20000 to 300,000, and more preferably 20000 to 100,000.
The larger the Mw of the polymer A, the higher the tensile strength of the protective layer obtained by curing the resin composition. Therefore, the handleability when peeling the integrated protective layer and the printing ink layer from the mount tends to be excellent. be.
The smaller the Mw of the polymer A, the better the solubility of the polymer A in the polymerizable compound. Further, since the viscosity of the resin composition is sufficiently low, the film forming property tends to be excellent when the protective layer is formed by a method such as printing.

The glass transition temperature of the polymer A is preferably 10 ° C. or higher, more preferably 20 to 70 ° C.
The higher the glass transition temperature of the polymer A, the less sticky the protective layer obtained by curing the resin composition becomes, and the better the blocking resistance. The lower the glass transition temperature, the better the tensile strength of the cured product.

The content ratio of the polymer A to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.
When the content ratio of the polymer A is in the range of 10 to 60% by mass with respect to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D, the bubbles in the protective layer can be further reduced. Moreover, the strength of the protective layer is further improved.
The larger the content ratio of the polymer A to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D, the easier it is for the resin composition to cure.
Further, the smaller the content ratio of the polymer A with respect to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D, the lower the viscosity of the resin composition and the better the printability.

The polymer A can be produced by a polymerization method such as suspension polymerization, solution polymerization, bulk polymerization, or emulsion polymerization.
Since the obtained polymer A has advantages such as easy high molecular weight, high degree of freedom in solvent selection of the resin composition, high solidification of the resin composition, and solvent-free resin composition. Suspension polymerization is preferable because the polymer A can be obtained as solid beads.

<Compound B>
Compound B is a polymerizable compound other than polymer A having one or more polymerizable double bonds in the molecule.

Compound B has a monofunctional monomer having one polymerizable double bond in the molecule (hereinafter, may be referred to as “Compound B1”) and two or more polymerizable double bonds in the molecule. At least one selected from the group consisting of polyfunctional monomers (hereinafter, may be referred to as "Compound B2") is preferable.
Compound B is not limited to one type, and may be two or more types.

Since the maximum point elongation of the cured product of the resin composition becomes better, the compound B preferably contains one or more of the compound B1 and one or more of the compound B2.

Specific examples of compound B1 are listed below, but compound B1 is not limited thereto.
Styrene compounds: styrene, α-methylstyrene, chlorostyrene.
Alkyl (meth) acrylate: Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate.
Alkoxyalkyl (meth) acrylate: methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate.
Allyloxyalkyl (meth) acrylate: Phenoxyethyl (meth) acrylate.
Hydroxyalkyl (meth) acrylate: 2-Hydroxyethyl (meth) acrylate.
Heterocyclic-containing (meth) acrylates: tetrahydrofurfuryl (meth) acrylates, cyclohexyl (meth) acrylates, isobornyl (meth) acrylates, (meth) acryloylmorpholins.

Examples of compound B1 include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and t. -Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, At least one selected from the group consisting of isobornyl (meth) acrylate and (meth) acryloylmorpholine is preferred.
From the viewpoint of improving the ultraviolet curability and the tensile strength of the protective layer, the compound B1 includes n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate and ( More preferably, at least one selected from the group consisting of meta) acryloylmorpholin.
The compound B1 is not limited to one type, and may be two or more types.

The content ratio of compound B1 is preferably 5.0 to 65.0% by mass, more preferably 10.0 to 65.0% by mass, and 15.0 to 65.0% by mass with respect to 100% by mass of the resin composition. Is more preferable, 20.0 to 65.0% by mass is particularly preferable, and 25.0 to 65.0% by mass is most preferable.
The higher the content ratio of the compound B1, the better the solubility of the acrylic polymer in the compound B1. Further, the smaller the content ratio of the compound B1, the higher the tensile strength of the protective layer obtained by curing the resin composition.

Compound B2 includes a polymerizable compound having two polymerizable double bonds in the molecule (hereinafter, may be referred to as “Compound B3”) and a polymerization having three or more polymerizable double bonds in the molecule. At least one selected from the group consisting of sex compounds (hereinafter, may be referred to as "Compound B4") is preferable.

Specific examples of compound B3 are listed below, but compound B3 is not limited thereto.
Alkylene glycol di (meth) acrylate: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate.
Oxyalkylene glycol di (meth) acrylate: Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, di. Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.
Aliphatic urethane (meth) acrylate.
Aromatic urethane (meth) acrylate.
Polyester (meth) acrylate.
Epoxy (meth) acrylate.

Examples of compound B3 include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and dipropylene glycol di (dipropylene glycol di (meth) acrylate. At least one selected from the group consisting of meta) acrylate, polypropylene glycol di (meth) acrylate, aliphatic urethane (meth) acrylate, aromatic urethane (meth) acrylate, polyester (meth) acrylate and epoxy (meth) acrylate. preferable.
From the viewpoint of improving the ultraviolet curability and the tensile strength of the protective layer, the compound B3 includes triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, aliphatic urethane (meth) acrylate, and aromatic urethane ( At least one selected from the group consisting of meta) acrylate, polyester (meth) acrylate and epoxy (meth) acrylate is more preferable, and aliphatic urethane (meth) acrylate, aromatic urethane (meth) acrylate, polyester (meth) acrylate. And at least one selected from the group consisting of epoxy (meth) acrylates is even more preferred.
Compound B3 is not limited to one type, and may be two or more types.

Specific examples of compound B4 are listed below, but compound B4 is not limited thereto.
Poly (meth) acrylates of trihydric or higher aliphatic polyhydric alcohols: trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate.
Aliphatic urethane (meth) acrylate.
Aromatic urethane (meth) acrylate.
Polyester (meth) acrylate.
Epoxy (meth) acrylate.

The compound B4 is a group consisting of an aliphatic urethane (meth) acrylate, an aromatic urethane (meth) acrylate, a polyester (meth) acrylate and an epoxy (meth) acrylate from the viewpoint of improving the ultraviolet curability and the tensile strength of the protective layer. At least one selected from is preferred.
The compound B4 is not limited to one type, and may be two or more types.

When a large amount of compound B4 is used as compound B, the flexibility of the protective layer obtained by curing the resin composition is lowered, and the calcinability is not positively affected. Therefore, the amount of compound B4 used is high. , Preferably a small amount. From the viewpoint of improving the flexibility and calcinability of the protective layer, the content ratio of the compound B4 in the compound B is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.

The content ratio of the compound B to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D is preferably 20 to 90% by mass, more preferably 40 to 65% by mass.
The larger the content ratio of the compound B with respect to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D, the lower the viscosity of the resin composition and the better the printability. Further, the smaller the content ratio of the compound B with respect to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D, the better the ultraviolet curability of the resin composition.

<Initiator C>
Initiator C is a compound that generates radicals under mild reaction conditions in order to proceed with a radical reaction, and is used as a polymerization initiator in a radical polymerization reaction.

Specific examples of the initiator C are shown below, but the initiator C is not limited thereto.
Benzophenones: Benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, 2-t-butylanthraquinone, 2-ethylanthraquinone.
Thioxanthones: 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone.
Acetophenones: Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) Propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone.
Benzoin ethers: benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether.
Acylphosphine oxides: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl)- Phosphine oxide.
Methylbenzoylformate.
1,7-bisacridinyl heptane.
9-Phenylacridine.
The initiator C is not limited to one type, and may be two or more types.

The content ratio of the initiator C with respect to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D is preferably 0.5 to 30% by mass, more preferably 5.0 to 25% by mass.
The larger the content ratio of the initiator C to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D, the better the curability of the resin composition. Further, the smaller the content ratio of the initiator C with respect to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D, the higher the strength of the protective layer obtained by curing the resin composition.

<Defoamer D>
The defoaming agent D is an additive that prevents the generation of bubbles and breaks the generated bubbles.

Specific examples of the defoaming agent D are shown below, but the defoaming agent D is not limited thereto.
Silicone-based antifoaming agent containing polysiloxane as an active ingredient: polyalkyldimethylsiloxane, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified siloxane , Polydimethylsiloxane containing polyester-modified hydroxyl group.
A non-silicone polymer defoamer containing a polymer such as an acrylic compound as an active ingredient.
A mineral oil-based defoamer in which hydrophobic particles are dispersed in carrier oil.

As the defoaming agent D, at least one selected from the group consisting of silicone-based defoaming agents and non-silicone-polymer-based defoaming agents is preferable from the viewpoint of film-forming property, and polyalkyldimethylsiloxane is used as an active ingredient. At least one selected from the group consisting of a silicone-based defoaming agent and a non-silicone-polymer-based defoaming agent containing an acrylic compound as an active ingredient is more preferable.
The defoaming agent D is not limited to one type, and may be two or more types.

The content ratio of the defoaming agent D with respect to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass.
The larger the content ratio of the defoaming agent D to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D, the smaller the number of bubbles in the protective layer obtained by curing the resin composition. Further, the smaller the content ratio of the defoaming agent D with respect to the total mass of the polymer A, the compound B, the initiator C and the defoaming agent D, the higher the tensile strength of the protective layer obtained by curing the resin composition. ..

<Other ingredients E>
Examples of the other component E (components other than the polymer A, the compound B, the initiator C and the defoaming agent D) include a thixotropic agent, a resin other than the polymer A, a plasticizer, and a solvent.

The thixotropy is an auxiliary agent for satisfying viscosity stability, flexibility, drying property, etc. at the time of application in printing or the like.
Examples of the thixotropy include fatty acid amide wax, amide wax, castor oil, and hydrogenated castor oil.

Examples of the resin other than the polymer A include an acrylic resin, a vinyl acetate resin, an alkyd resin, a polyester resin, and a cellulosic resin.
As the resin other than the polymer A, an acrylic resin is preferable. Acrylic resins have a wide variety of raw material monomers and can be copolymerized in any combination, so that the degree of freedom in designing the glass transition temperature and molecular weight is high.
When the resin composition contains an acrylic resin, the printability of the resin composition becomes more excellent, and further, the physical properties of the coating film of the protective layer obtained by curing the resin composition become easier to adjust.

Further, in order to improve the flexibility of the protective layer, the resin composition may contain a plasticizer. Examples of the plasticizer include phthalates, phosphates, adipates, ether compounds, and paraffin compounds. Examples of the phthalate ester include phthalate dialkyl esters such as dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate; alkylbenzyl phthalate such as butylbenzyl phthalate; alkylaryl phthalate; phthalic acid. Dibenzyl; Diaryl phthalate and the like can be mentioned. Examples of the phosphoric acid ester include a triaryl phosphate type such as tricresyl phosphate, a trialkyl phosphate type, and an alkylaryl phosphate type phosphoric acid ester. Examples of the adipate ester include aliphatic dibasic acid esters such as dibutyl adipate and dioctyl adipate. Examples of the ether compound include polyethylene glycol, polypropylene glycol, dibutyl glycol adipate and the like. Examples of the paraffin compound include liquid paraffin and paraffin wax. Paraffin wax can be added as a plasticizer. Paraffin wax can also be added for the purpose of enhancing UV curability by blocking oxygen. In addition, soybean oil such as polyester-based soybean oil and epoxidized soybean oil can also be used as a plasticizer.

Further, in order to improve the solubility of the acrylic polymer A, the resin composition may contain a solvent. Specific examples of the solvent are shown below, but the solvent is not limited thereto.
Aromatic solvents: toluene, xylene, ethylbenzene.
Acetic acid ester solvent: ethyl acetate, normal butyl acetate, isobutyl acetate, normal propyl acetate, isopropyl acetate, amyl acetate.
Ketone solvent: methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, acetone.
Alcohol-based solvents: methanol, ethanol, isopropyl alcohol, normal propyl alcohol, normal butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, benzyl alcohol, diacetone alcohol, dipropylene glycol n-propyl ether, dipropylene glycol methyl ether, propylene glycol n-propyl ether.
Glycol solvent: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol.
Glycol ether solvent: ethylene glycol monoethyl ether, ethylene glycol monobutyl ether.
Acetate solvent: Methyl cellosolve acetate, methoxypropyl acetate.
Hydrocarbon solvents: normal hexane, cyclohexane, methylcyclohexane, heptane.
Naphthenic solvent: Exor (registered trademark) D80, Exor D110, Exor D130 (all manufactured by ExxonMobil).
Paraffin-based solvent: Isopar (registered trademark) H, Isopar L, Isopar M (all manufactured by ExxonMobil).
Naphtha-based solvent: Solbesso (registered trademark) 100, Solbesso 150, Solbesso 200 (above, ExxonMobil), Swazole (registered trademark) 1000, Swazol 1500, Swazol 1800 (above, manufactured by Maruzen Petroleum), Ipsol (registered trademark) ) 100, Ipsol 150 (all manufactured by Idemitsu Kosan Co., Ltd.).

The content ratio of the other component E to the total mass of the polymer A is preferably 15% by mass or less, more preferably 10% by mass or less.
The smaller the content ratio of the other component E to the total mass of the polymer A, the better the coating suitability when the resin composition is applied by screen printing or the like to form a protective layer.

<Viscosity of resin composition>
The viscosity of the resin composition is preferably 0.1 to 100 Pa · s, more preferably 1 to 50 Pa · s.
The lower the viscosity of the resin composition, the better the coating suitability when the resin composition is applied by screen printing or the like to form a protective layer. Further, the higher the viscosity of the resin composition, the thicker the coating film formed by applying the resin composition by screen printing or the like, and it becomes easier to arrange the protective layer with the printing ink layer on ceramics or the like.

<Manufacturing method of resin composition>
The resin composition can be produced by blending the polymer A and the compound B. At this time, if necessary, one or more selected from the group consisting of the initiator C, the defoaming agent D, and the other component E may be further blended.
The formulation of each component can be carried out by mixing with a commonly known stirrer.

As a method for producing the resin composition, for example, the compound B is charged into a mixing device equipped with a stirrer, a cooling tube, and a thermometer, and the polymer A is gradually added while stirring the compound B to dissolve the polymer A. After confirming that, a method of adding the initiator C, the defoaming agent D, and if desired, the other component E can be mentioned.
Polymer A, initiator C, defoamer D and other component E may be blended with compound B.

[Laminate, transfer paper for painting]
The laminate is a stack of a mount, a water-soluble paste layer, a printing ink layer, and a protective layer in this order.
The protective layer is a cured product of the resin composition.

The transfer paper for painting is made of a laminated body.
Hereinafter, an embodiment of the transfer paper for painting will be described with reference to FIG. 1 as appropriate.

FIG. 1 is a schematic cross-sectional view showing an example of a transfer paper for painting.

The painting transfer paper 1 of the present embodiment is a stack of a mount 3, a water-soluble paste layer 5, a printing ink layer 7, and a protective layer 9 in this order.
The water-soluble paste layer 5 is formed so as to cover the entire surface of the mount 3.
The printing ink layer 7 is partially formed on the water-soluble paste layer 5.
The protective layer 9 is formed so as to cover the printing ink layer 7. A part of the protective layer 9 is in contact with the water-soluble paste layer 5.

As the mount 3, a paper having good water absorption is preferable.
Examples of paper having good water absorption include Japanese paper.

Examples of the water-soluble paste that forms the water-soluble paste layer 5 include starch, polyvinyl alcohol, and carboxymethyl cellulose.

Examples of the ink forming the printing ink layer 7 include thermosetting inks, thermoplastic inks, and ultraviolet curable inks.
The printing ink layer 7 is formed of a pattern transferred to ceramics or the like.
The printing ink layer 7 may be a single layer or a multilayer.
The printing ink layer 7 can be formed by a known method. For example, the printing ink layer 7 can be formed by applying ink on the water-soluble adhesive layer 5 by screen printing, gravure printing, flexographic printing, offset printing, or the like and curing it if necessary.

The protective layer 9 is made of a cured product of the resin composition.
The cured product of the resin composition is preferably formed by applying the resin composition on the printing ink layer 7 and irradiating it with ultraviolet rays to cure it.
Examples of the method for applying the resin composition include screen printing, gravure printing, flexographic printing, and offset printing.
Examples of the light source of ultraviolet rays include solar rays, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, and LED lamps. As the light source of ultraviolet rays, a high-pressure mercury lamp, a metal halide lamp, and an LED lamp are preferable from the viewpoint of ultraviolet curability.
The irradiation energy density of ultraviolet rays is preferably ^{50 to 1500 mJ / cm 2.}
The atmosphere when the resin composition is irradiated with ultraviolet rays and cured may be either an oxidative atmosphere or a non-oxidative atmosphere. Specifically, the atmosphere may be any of air, hydrogen, nitrogen, and a rare gas such as argon.

In the painting transfer paper 1, for example, a printing ink layer 7 is formed by using ink on a mount 3 on which a water-soluble paste is applied to the entire surface to form a water-soluble paste layer 5, and the printing ink layer 7 is formed on the mount 3. It can be produced by applying a resin composition to the ink and curing it to form a protective layer 9.

Using the painting transfer paper 1, for example, the ceramics can be painted as follows.
First, the transfer paper 1 for painting is immersed in water or warm water to dissolve the water-soluble paste layer 5, and the protective layer 9 with the printing ink layer 7 is peeled off from the mount 3. The protective layer 9 with the printing ink layer 7 is arranged at a predetermined position on the ceramic so that the ceramic and the printing ink layer 7 are in contact with each other. Then, after removing water and air bubbles between the protective layer 9 with the printing ink layer 7 and the ceramics, when the protective layer 9 is fired, the printing ink layer 7 remains on the surface of the ceramics and the ceramics are painted. Will be printed.

The above-described embodiment has been described with an example of applying the painting transfer paper 1 to ceramics, but the painting transfer paper 1 can be applied to other than ceramics, for example, liquor bottles and food bottles.

Although the embodiment of the transfer paper for painting has been described above by showing an example, the present invention is not limited to the above embodiment. Each configuration and a combination thereof in the above-described embodiment are examples, and the configurations can be added, omitted, replaced, and other changes as long as they do not deviate from the gist of the present invention.

For example, the water-soluble paste layer 5 may be provided at least at a position where the printing ink layer 7 and the protective layer 9 are formed, and may not cover the entire surface of the mount 3.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples described later, and various modifications can be made without departing from the gist of the present invention.
In Examples and Comparative Examples, "parts" means "parts by mass" and "%" means "% by mass".
The various conditions and the values of the evaluation results in the following examples indicate a suitable numerical range as in the preferable numerical range in the embodiment disclosed in the present specification, and the preferable range of the present invention is the embodiment. It can be determined in consideration of the preferable numerical range in 1 and the range indicated by the combination of the values of the following examples or the values of the examples.

[Evaluation method]
<Solubility>
The polymer A, the compound B, the initiator C and the defoaming agent D are blended in the number of copies shown in Table 1 or Table 2, and the compound B is charged in a mixing device equipped with a stirrer, a cooling tube and a thermometer. The polymer A was added little by little while stirring with a stirrer at an internal temperature of 25 ° C. and 300 rpm for 10 minutes, and then the mixture was stirred at an internal temperature of 50 ° C. and 300 rpm for 60 minutes. Then, the initiator C and the defoaming agent D were added, and the mixture was stirred at an internal temperature of 40 ° C. and 300 rpm for 30 minutes.
The solubility of the mixture was evaluated according to the following evaluation criteria.

(Evaluation criteria)
A: There is no residual solid matter visually.
C: There is a residual solid matter visually.

<Tensile strength>
Using a cylinder printing machine, the prepared resin composition is printed on a mount (SPA, manufactured by Murakami Co., Ltd .; 215 mm x 290 mm) on which the water-soluble paste is uniformly applied on the entire surface, and the resin is printed on a nylon 80 mesh screen. A coating film of the composition was formed and cured by ultraviolet rays. Then, the protective layer was peeled off from the mount in water.
The peeled protective layer was punched out with a dumbbell type 2 (JIS K 6251: 2017) to prepare a test piece.
The prepared test piece was subjected to a tensile test using a tensile measuring device (Autograph AG-5kNIS, manufactured by Shimadzu Corporation) under the conditions of a test temperature of 23 ° C. and a test speed of 10 mm / min, and the maximum point elongation was measured. ..
The tensile strength of the protective layer was evaluated according to the following evaluation criteria.

(Evaluation criteria)
A: The maximum point elongation is 100% or more.
B: The maximum point elongation is 50% or more and less than 100%.
C: The maximum point elongation is less than 50%.

[How to make a laminate (transfer paper for painting)]
Using a cylinder printing machine, 12 parts of UV-curable medium (803068, FERRO) and red pigment (803068, FERRO) are printed on a mount (SPA, manufactured by Murakami; 215 mm x 290 mm) in which a water-soluble paste is uniformly applied to the entire surface. A UV curable ink prepared by mixing 15 parts (34634, manufactured by IZAWA) was printed on a nylon 300 mesh screen to form a printing ink layer having a floral pattern, and UV curing was performed. Next, the resin composition was printed on it with a nylon 80-mesh screen to form a coating film of the resin composition, which was then cured by ultraviolet rays to form a protective layer.

The conditions for UV curing of the printing ink layer are as follows.
Equipment: USX5-0902 (manufactured by Eye Graphics).
Conditions: Light source High pressure mercury lamp (120W).
Ultraviolet illuminance 450 mW / cm ² .
Cumulative irradiation amount 400 mJ / cm ² (irradiation distance about 130 mm, belt feed rate 4.7 m / min).
The ultraviolet illuminance and the integrated irradiation amount were measured using an ultraviolet light meter (UV-351, manufactured by Oak Co., Ltd.).

The conditions for UV curing of the protective layer are as follows.
Equipment: USX5-0902 (manufactured by Eye Graphics).
Conditions: Light source High pressure mercury lamp (120W).
Ultraviolet illuminance 520 mW / cm ² .
Cumulative irradiation amount 590 mJ / cm ² (irradiation distance about 130 mm, belt feed rate 3.0 m / min).
The ultraviolet illuminance and the integrated irradiation amount were measured using an ultraviolet light meter (UV-351, manufactured by Oak Co., Ltd.).

<Burning property>
The laminated body (transfer paper for painting) is immersed in water to peel off the integrated protective layer and printing ink layer from the mount, and the printing ink layer is brought into contact with the plate to be attached and dried, and then ultra-high speed. It was fired at 780 ° C. for 20 minutes using a heating electric furnace (S6-2025D, manufactured by Motoyama Co., Ltd.), and the printing state on the plate was visually observed.
The calcinability of the protective layer was evaluated according to the following evaluation criteria.

(Evaluation criteria)
A: After firing, there were no pinholes and a floral pattern was printed.
C: After firing, pinholes were generated in the floral pattern.
The ultraviolet curing in the evaluation of the calcinability was performed under the same conditions as the ultraviolet curing of the printing ink layer.

[Manufacturing method of dispersant]
900 parts of deionized water, 60 parts of 2-sulfoethyl sodium methacrylate, 10 parts of potassium methacrylate and 12 parts of methyl methacrylate are placed in a polymerization apparatus equipped with a stirrer, a cooling tube and a thermometer, and the mixture is stirred and stirred. The temperature was raised to 50 ° C. while replacing the inside with nitrogen. 0.08 part of a polymerization initiator (2,2'-azobis (2-methylpropionamidine) dihydrochloride) was added thereto, and the temperature was further raised to 60 ° C. After the temperature was raised, methyl methacrylate was continuously added dropwise at a rate of 0.24 part / min for 75 minutes using a dropping pump. After completion of the dropping, the reaction solution was held at 60 ° C. for 6 hours and then cooled to room temperature to obtain a dispersant having a solid content of 10%, which is a transparent aqueous solution.

[Synthesis of acrylic polymer]
<Synthesis Example 1: Polymer A1>
In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.3 part of sodium sulfate, and 0.3 part of a dispersant (solid content 10%) are put and stirred to make a uniform aqueous solution. And said. Next, 81 parts of isobutyl methacrylate, 19 parts of 2-ethylhexyl methacrylate, 0.2 parts of dodecyl mercaptan, and 0.3 parts of 2,2'-azobis (2-methylbutyronitrile) were added. , An aqueous suspension.
Next, the inside of the polymerization apparatus was replaced with nitrogen, the temperature was raised to 80 ° C. and reacted for 1 hour, and in order to further increase the polymerization rate, the temperature was raised to 90 ° C. and held for 1 hour. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing a polymer. The aqueous suspension was filtered through a nylon filter cloth having a mesh size of 45 μm, the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain 90 parts of polymer A1.

The polymer A1 contained 100% of the monomer units derived from the branched alkyl (meth) acrylate with respect to the total mass of all the monomer units constituting the polymer A1. The breakdown was 81% for the monomer unit derived from isobutyl methacrylate and 19% for the monomer unit derived from 2-ethylhexyl methacrylate.
The glass transition temperature of the polymer A1 was 35 ° C., and the mass average molecular weight was 110,000.

<Synthesis Example 2: Polymer A2>
In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.2 part of sodium sulfate, and 0.3 part of a dispersant (solid content 10%) are put and stirred to make a uniform aqueous solution. And said. Next, 50 parts of isobutyl methacrylate, 50 parts of n-butyl methacrylate, 0.13 part of dodecyl mercaptan, and 0.3 part of 2,2'-azobis (2-methylbutyronitrile) were added. , An aqueous suspension.
Next, the inside of the polymerization apparatus was replaced with nitrogen, the temperature was raised to 85 ° C. and reacted for 1 hour, and in order to further increase the polymerization rate, the temperature was raised to 95 ° C. and held for 30 minutes. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing a polymer. The aqueous suspension was filtered through a nylon filter cloth having a mesh size of 45 μm, the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain 90 parts of polymer A2.

The polymer A2 contained 50% of the monomer units derived from the branched alkyl (meth) acrylate with respect to the total mass of all the monomer units constituting the polymer A2. The breakdown was 50% of the monomer unit derived from isobutyl methacrylate and 50% of the monomer unit derived from n-butyl methacrylate.
The glass transition temperature of the polymer A2 was 33 ° C., and the mass average molecular weight was 190000.

<Synthesis Example 3: Polymer A3>
In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.2 part of sodium sulfate, and 0.3 part of a dispersant (solid content 10%) are put and stirred to make a uniform aqueous solution. And said. Next, 85 parts of isobutyl methacrylate, 15 parts of 2-ethylhexyl methacrylate, 0.3 parts of dodecyl mercaptan, and 0.3 parts of 2,2'-azobis (2-methylbutyronitrile) were added. , An aqueous suspension.
Next, the inside of the polymerization apparatus was replaced with nitrogen, the temperature was raised to 85 ° C. and reacted for 1 hour, and in order to further increase the polymerization rate, the temperature was raised to 95 ° C. and held for 30 minutes. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing a polymer. The aqueous suspension was filtered through a nylon filter cloth having a mesh size of 45 μm, the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain 90 parts of polymer A3.

The polymer A3 contained 100% of the monomer units derived from the branched alkyl (meth) acrylate with respect to the total mass of all the monomer units constituting the polymer A3. The breakdown was 85% of the monomer unit derived from isobutyl methacrylate and 15% of the monomer unit derived from 2-ethylhexyl methacrylate.
The glass transition temperature of the polymer A3 was 38 ° C., and the mass average molecular weight was 70,000.

<Synthesis Example 4: Polymer A4>
In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.2 part of sodium sulfate, and 0.3 part of a dispersant (solid content 10%) are put and stirred to make a uniform aqueous solution. And said. Next, 100 parts of isobutyl methacrylate, 0.3 part of dodecyl mercaptan, and 1.2 part of 2,2'-azobis (2-methylbutyronitrile) were added to prepare an aqueous suspension.
Next, the inside of the polymerization apparatus was replaced with nitrogen, the temperature was raised to 85 ° C. and reacted for 1 hour, and in order to further increase the polymerization rate, the temperature was raised to 95 ° C. and held for 30 minutes. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing a polymer. The aqueous suspension was filtered through a nylon filter cloth having a mesh size of 45 μm, the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain 92 parts of polymer A4.

The polymer A4 contained 100% of the monomer units derived from the branched alkyl (meth) acrylate with respect to the total mass of all the monomer units constituting the polymer A4. The breakdown was 100% of the monomer unit derived from isobutyl methacrylate.
The glass transition temperature of the polymer A4 was 48 ° C., and the mass average molecular weight was 22000.

<Synthesis Example 5: Polymer A5>
In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.2 part of sodium sulfate, and 0.3 part of a dispersant (solid content 10%) are put and stirred to make a uniform aqueous solution. And said. Next, 20 parts of isobutyl methacrylate, 80 parts of n-butyl methacrylate, 0.05 part of octyl mercaptan, and 0.15 part of 2,2'-azobis (2-methylbutyronitrile) were added. , Aqueous suspension.
Next, the inside of the polymerization apparatus was replaced with nitrogen, the temperature was raised to 85 ° C. and reacted for 1 hour, and in order to further increase the polymerization rate, the temperature was raised to 95 ° C. and held for 30 minutes. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing a polymer. The aqueous suspension was filtered through a nylon filter cloth having a mesh size of 45 μm, the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain 90 parts of polymer A5.

The polymer A5 contained 20% of the monomer units derived from the branched alkyl (meth) acrylate with respect to the total mass of all the monomer units constituting the polymer A5. The breakdown was 20% for the monomer unit derived from isobutyl methacrylate and 80% for the monomer unit derived from n-butyl methacrylate.
The glass transition temperature of the polymer A5 was 25 ° C., and the mass average molecular weight was 260000.

<Synthesis Example 6: Comparative Polymer A6>
In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.2 part of sodium sulfate, and 0.3 part of a dispersant (solid content 10%) are put and stirred to make a uniform aqueous solution. And said. Next, 20 parts of methyl methacrylate, 80 parts of n-butyl methacrylate, 0.17 part of dodecyl mercaptan, and 0.3 part of 2,2'-azobis (2-methylbutyronitrile) were added. , Aqueous suspension.
Next, the inside of the polymerization apparatus was replaced with nitrogen, the temperature was raised to 75 ° C. and reacted for 1 hour, and in order to further increase the polymerization rate, the temperature was raised to 95 ° C. and held for 30 minutes. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing a polymer. The aqueous suspension was filtered through a nylon filter cloth having a mesh size of 45 μm, the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain 90 parts of Comparative Polymer A6.

The comparative polymer A6 did not contain monomeric units derived from branched alkyl (meth) acrylates. The breakdown was 20% of the monomer unit derived from methyl methacrylate and 80% of the monomer unit derived from n-butyl methacrylate.
The glass transition temperature of the comparative polymer A6 was 34 ° C., and the mass average molecular weight was 130000.

<Synthesis Example 7: Comparative Polymer A7>
In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate, and 0.3 part of a dispersant (solid content 10%) are put and stirred to make a uniform aqueous solution. And said. Next, 100 parts of isobutyl methacrylate and 0.1 part of 2,2'-azobis (2-methylbutyronitrile) were added to prepare an aqueous suspension.
Next, the inside of the polymerization apparatus was replaced with nitrogen, the temperature was raised to 80 ° C. and reacted for 1 hour, and in order to further increase the polymerization rate, the temperature was raised to 90 ° C. and held for 60 minutes. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing a polymer. The aqueous suspension was filtered through a nylon filter cloth having a mesh size of 45 μm, the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain 92 parts of Comparative Polymer A7.

The comparative polymer A7 contained 100% of monomer units derived from the branched alkyl (meth) acrylate. The breakdown was 100% of the monomer unit derived from isobutyl methacrylate.
The glass transition temperature of the comparative polymer A7 was 48 ° C., and the mass average molecular weight was 460000.

[Examples 1 to 17, Comparative Examples 1 to 2]
Each component was blended in the blending amount (part) shown in Table 1 or Table 2 and mixed with a high-speed disperser to produce a resin composition.
In each example, the solubility, tensile strength and calcinability were evaluated according to the above-mentioned evaluation method, and the evaluation results are shown in the corresponding columns of Table 1 or Table 2.

● Acrylic polymer Polymer A1: The acrylic polymer synthesized in Synthesis Example 1 (IBMA / EHMA = 81/19 (ratio of mass% in polymer); Mw = 110,000).
Polymer A2: The acrylic polymer synthesized in Synthesis Example 2 (IBMA / BMA = 50/50 (ratio of mass% in polymer); Mw = 190000).
Polymer A3: The acrylic polymer synthesized in Synthesis Example 3 (IBMA / EHMA = 85/15 (ratio of mass% in polymer); Mw = 70000).
Polymer A4: The acrylic polymer synthesized in Synthesis Example 4 (IBMA = 100 (mass% in polymer); Mw = 22000).
Polymer A5: Acrylic polymer synthesized in Synthesis Example 5 (IBMA / BMA = 20/80; (ratio of mass% in polymer) Mw = 260000).
Comparative polymer A6: The acrylic polymer synthesized in Synthesis Example 6 (MMA / BMA = 20/80 (ratio of mass% in polymer); Mw = 130000).
Comparative polymer A7: The acrylic polymer synthesized in Synthesis Example 7 (IBMA = 100 (mass% in polymer); Mw = 460000).

● Polymerizable compound Compound B1-1: 2-ethylhexyl acrylate.
Compound B1-2: n-butyl acrylate.
Compound B1-3: n-Butyl methacrylate.
Compound B3-1: Triethylene glycol dimethacrylate.
Compound B3-2: Bifunctional aliphatic urethane acrylate (100% active ingredient). (EBECRYL8402, manufactured by Daicel Ornex).

● Initiator Initiator C1: 1-Hydroxycyclohexyl-phenylketone.
Initiator C2: Benzophenone.

● Defoaming agent Defoaming agent D1: Silicone-based defoaming agent (active ingredient 0.7%; solvent: diisobutyl ketone) (BYK (registered trademark) -066N, manufactured by Big Chemie Japan Co., Ltd.).

● Plasticizer Plasticizer E1: Paraffin wax P115 (manufactured by Nippon Seiro Co., Ltd.).
Plasticizer E2: Monosizer PB-3A (manufactured by DIC Corporation).

"ND" in Table 2 indicates that measurement was not possible. No evaluation.

The resin compositions of Examples 1 to 17 were all excellent in the evaluation of the solubility of the composition and the tensile strength and calcinability of the cured product.
On the other hand, in Comparative Example 1, since the monomer unit of the acrylic polymer is the monomer unit derived from linear methyl methacrylate and the monomer unit derived from n-butyl methacrylate, the calcinability of the cured product Was not enough.
In Comparative Example 2, since the mass average molecular weight of the acrylic polymer was larger than 450,000, the solubility of the composition was poor, and the tensile strength and calcinability of the cured product could not be evaluated.

1 ... Transfer paper for painting, 3 ... Mount, 5 ... Water-soluble glue layer, 7 ... Printing ink layer, 9 ... Protective layer

According to the resin composition for an ultraviolet curable transfer paper protective layer of the present invention, a protective layer having excellent calcinability can be formed during the production of a transfer paper for painting.
The laminate of the present invention has a protective layer having excellent calcinability.
The transfer paper for painting of the present invention has a protective layer having excellent calcinability.

Claims (9)

1. Contains an acrylic polymer and a polymerizable compound,
   The acrylic polymer contains a monomer unit derived from an alkyl (meth) acrylate having a branched alkyl group.
   The mass average molecular weight of the acrylic polymer is 20000 to 450,000.
   The polymerizable compound is a resin composition for an ultraviolet curable transfer paper protective layer having one or more polymerizable double bonds in the molecule.
2. The resin composition for an ultraviolet curable transfer paper protective layer according to claim 1, wherein the acrylic polymer has a mass average molecular weight of 20000 to 100,000.
3. Claimed that the content ratio of the monomer unit derived from the alkyl (meth) acrylate having a branched alkyl group is 5 to 100% with respect to 100% by mass of all the monomer units of the acrylic polymer. Item 2. The resin composition for an ultraviolet curable transfer paper protective layer according to Item 1 or 2.
4. The monomer unit derived from the alkyl (meth) acrylate having a branched alkyl group is a monomer unit derived from isobutyl (meth) acrylate, a monomer unit derived from sec-butyl (meth) acrylate, and the like. The resin composition for an ultraviolet curable transfer paper protective layer according to any one of claims 1 to 3, which comprises at least one selected from the group consisting of monomer units derived from 2-ethylhexyl methacrylate.
5. The resin composition for an ultraviolet curable transfer paper protective layer according to any one of claims 1 to 4, wherein the polymerizable compound contains a monofunctional monomer and a polyfunctional monomer.
6. Claimed that the polyfunctional monomer is at least one selected from the group consisting of an aliphatic urethane (meth) acrylate, an aromatic urethane (meth) acrylate, a polyester (meth) acrylate and an epoxy (meth) acrylate. Item 5. The resin composition for an ultraviolet curable transfer paper protective layer according to Item 5.
7. The UV curable according to claim 5 or 6, wherein the content ratio of the monofunctional monomer is 5.0 to 65.0 mass% with respect to 100 mass% of the resin composition for the UV curable transfer paper protective layer. A resin composition for a protective layer for sex transfer paper.
8. Mount and
   With a water-soluble glue layer,
   Printing ink layer and
   A protective layer made of a cured product of the resin composition for an ultraviolet curable transfer paper protective layer according to any one of claims 1 to 7.
   Is a laminated body laminated in this order.
9. A transfer paper for painting made of the laminate according to claim 8.

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