JP6776637B2 - UV ink made of active energy ray-polymerizable composition and its production method - Google Patents

Description

The present invention relates to an active energy ray-polymerizable composition containing a polymer having a (meth) acryloyl group in a side chain, a polymer of a component of the composition, a method for producing the composition, and a UV ink comprising the composition. Further, the present invention relates to a cured product obtained by irradiating the composition with active energy rays.

The active energy ray-polymerizable composition has a property of being cured by polymerization in a short time by active energy rays such as ultraviolet rays, and the cured product has excellent transparency, and the cured product has toughness, flexibility, scratch resistance, and scratch resistance. It has excellent properties such as chemical properties.
From this point, the active energy ray-polymerizable composition is used in various fields such as a coating agent for a plastic base material, a UV ink, a lens molding material, a sealant, and an adhesive. For example, UV inks are widely applied in the printing industry such as flat papers, packaging, stickers and labels. The reason is that it reduces the environmental load compared to conventional solvent-drying inks, improves print quality and productivity, and is excellent in instant curing, high strength, low odor, reduced environmental load, and adhesion. It can be mentioned that it has such a point. On the other hand, disadvantages include high price, skin irritation, lithographic printing suitability, electrical energy consumption during exposure, and the like, and improvements thereof are desired.

For the purpose of improving these, compounds containing (meth) acrylate groups having a weight average molecular weight of 1000 or more as the main component of UV ink, for example, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, It is conceivable to use a polymer or the like having a (meth) acryloyl group in the side chain. In particular, a polymer having a (meth) acryloyl group in the side chain is considered to be advantageous for improvement such as improving curability and reducing curing shrinkage, but a polymer produced by a suspension polymerization method (Patent Document 1) is There is a problem that it is difficult to handle as a UV ink because the weight average molecular weight becomes 20000 or more and the viscosity of the resin becomes too high. Further, a polymer produced by solution polymerization (Patent Document 2) has a problem that the production cost is high because the polymerization needs to be performed at a high temperature and high pressure and a step of separating the solvent after the polymerization is required. there were.

International Publication No. 2012/093465 Japanese Unexamined Patent Publication No. 10-17812

An object of the present invention is an active energy ray-polymerizable composition having a low viscosity suitable for UV ink and the like, good curability, and little curing shrinkage, a polymer suitable for the components of the composition, and a method for producing the composition. The present invention is to provide a UV ink composed of the composition and a cured product of the composition.

The present invention is the invention according to the following [1] to [9].

[1] It contains at least one structure selected from the structures represented by the formulas (2) and (3) and the structure represented by the formula (1), and one end of the polymer main chain is the formula (4) and the formula ( A UV ink having an active energy ray-polymerizable composition having a structure selected from 5) and the formula (6) and containing a polymer (A) having a weight average molecular weight of 1000 or more and 20000 or less.

In the structures represented by the formulas (1) to (6), R ¹ represents any of a substituted or unsubstituted alkyl group, cycloalkyl group and aryl group, and R ² , R ²¹ and R ²² are independently hydrogen. Alternatively, it represents a methyl group, and R ³¹ and R ³² each independently represent either a substituted or unsubstituted alkylene group, a cycloalkylene group, or an arylene group. The substituent of R ¹ is any of an epoxy group, a hydroxy group, a cyano group, an isocyanate group, an amino group and a carboxyl group, and the substituents of R ³¹ and R ³² are an epoxy group, a hydroxy group, a cyano group and an isocyanate. It is either a group, an amino group or a carboxyl group. Further, n = 0 to 2.

[2] A UV ink comprising the active energy ray-polymerizable composition according to the above [1], wherein the polymer (A) has a weight average molecular weight of 1000 or more and 4900 or less.

[3] A UV ink comprising the active energy ray-polymerizable composition according to the above [1] or [2], wherein the (meth) acryloyl equivalent of the polymer (A) is 750 g / eq or more.

[4] A UV ink comprising the active energy ray-polymerizable composition according to any one of the above [1] to [3], wherein the polymer (A) is a polymer containing the structure of the formula (2).

[5] The polymer (A) is contained in an amount of 1 to 70% by mass, the monomer (C) having a polymerizable double bond is contained in an amount of 30 to 99% by mass, and the photopolymerization initiator (B) is contained in the polymerizable component 100. A UV ink comprising the active energy ray-polymerizable composition according to any one of [1] to [4] above, which contains 1 to 20 parts by mass with respect to parts by mass.

[6] The UV ink comprising the active energy ray-polymerizable composition according to any one of [1] to [5] above, wherein the solvent is 5 parts by mass or less with respect to 100 parts by mass of the polymerizable component.

[ 7 ] A polymer containing a glycidyl (meth) acrylate unit and / or a hydroxyl group-containing (meth) acrylate unit is dissolved in a monomer (C) having a polymerizable double bond, and the epoxy group and / or the epoxy group of the polymer and the polymer are dissolved. / Or The active energy according to any one of [1] to [6] above, which comprises a step of producing the polymer (A) by adding a compound containing a (meth) acryloyl group and a carboxyl group to a hydroxyl group. A method for producing a UV ink comprising a linearly polymerizable composition.

[ 8 ] A step of water-dispersing a polymer containing a glycidyl (meth) acrylate unit and adding a compound containing a (meth) acryloyl group and a carboxyl group to the epoxy group of the polymer to produce the polymer (A). The method for producing a UV ink comprising the active energy ray-polymerizable composition according to any one of [1] to [6] above.

The active energy ray-polymerizable composition of the present invention (hereinafter, also referred to as the present composition) has a low viscosity, good curability, and low curing shrinkage, and is therefore suitable for UV ink and the like. The polymer of the present invention is suitable as a component of the present composition. Further, the method for producing the present composition is economical because a polymer having a (meth) acryloyl group as a main component of the present composition in the side chain can be produced without performing a solvent removal step.

In the present specification, "(meth) acrylate" is a general term for "acrylate" and "methacrylate", and means one or both of acrylate and methacrylate. Similarly, "(meth) acryloyl group" is a general term for "acryloyl group" and "methacrylic acid group", and "(meth) acrylic acid" is a general term for "acrylic acid" and "methacrylic acid".

The present composition contains a polymer (A) having a (meth) acryloyl group in the side chain, and if necessary, a photopolymerization initiator (B) and a monomer (C) having a polymerizable double bond. Contains.

[Polymer having (meth) acryloyl group in the side chain (component A)]
The polymer (A) having a (meth) acryloyl group in the side chain (hereinafter referred to as component A) is a reactive polymer containing a structure represented by the formula (1). Further, the component A contains at least one structure represented by the formulas (2) and (3). The reason why the (meth) acrylic monomer unit is contained in the polymer main chain is that it is possible to exhibit excellent curability and transparency. Further, the component A needs to have one structure selected from the formulas (4), (5) and (6) in which one end of the polymer main chain contains a carbon-carbon double bond. In the present specification, the term "main chain" means the carbon chain having the largest number of carbon atoms in the reactive polymer.

Specific examples of the raw material monomer for introducing the structure represented by the formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and i-propyl (meth) acrylate. , N-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, i-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (Meta) acrylic acid esters such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. Hydroxyl group-containing (meth) acrylic acid ester; phenoxy (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, o -Aromatic ring-containing (meth) acrylic acid ester such as biphenyloxyethyl (meth) acrylate; glycidyl group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether; Examples thereof include (meth) acrylic monomers such as isocyanate group-containing (meth) acrylic acid esters such as meta) acrylic isocyanate and 2- (meth) acryloyloxyethyl isocyanate.

Among the (meth) acrylic monomers, methyl (meth) acrylate, ethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) from the viewpoint of exhibiting good curability. ) Acryloyl morpholine, isobornyl (meth) acrylate, benzyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate are preferable.

Further, the (meth) acrylic monomer unit of the formula (1) contained in the component A may be one kind or two or more kinds. However, since it is easy to precisely adjust the physical properties of the coating film when UV ink is used, the copolymer weight containing two or more kinds of (meth) acrylic monomer units of the formula (1). It is preferably coalesced.

Further, since the component A has the structure of the formula (2) and / or the formula (3), it has a (meth) acryloyloxy group in the side chain. In addition, in this specification, the term "side chain" means a chain structure branched from the main chain (carbon chain having the largest number of carbon atoms) of the reactive polymer.

The component A having a (meth) acryloyloxy group in the side chain has ultraviolet curability, and the polymers are crosslinked by ultraviolet irradiation, which contributes to the improvement of curability of the present composition. In addition, the component A also contributes to the preferable effects of improving the strength of the cured product of the present composition, reducing the odor, and improving the adhesion.

The component A contains a monomer unit other than the formulas (1), (2) and (3) (hereinafter, referred to as other monomer units) as long as the effect of the present invention is not impaired. There may be.

The raw material monomer of other monomer units is not particularly limited, and specific examples of such raw material monomer include aromatic vinyls such as styrene and α-methylstyrene; vinyl acetate and vinyl propionate. Unsaturated dicarboxylic acids such as vinyl carboxylate, maleic anhydride, itaconic acid, fumaric acid, etc .; N-vinyllactam such as N-vinylpyrrolidone, N-vinylcaprolactam; acrylic acid, methacrylate; ammonium (meth) acrylate. , (Meta) acrylates such as sodium (meth) acrylate, potassium (meth) acrylate; (meth) acrylamide, (meth) acryloylmorpholine, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, dimethylaminopropyl (Meta) acrylamide such as acrylamide and isopropyl (meth) acrylamide; (meth) acrylonitrile such as (meth) acrylonitrile; and the like can be mentioned.

The content of the (meth) acrylic monomer unit of the component A is preferably 50% by mass or more when the total of the monomer units constituting the main chain of the reactive polymer is 100% by mass. , 90% by mass or more, and particularly preferably 100% by mass. That is, it is particularly preferable that all of the main chains are composed of (meth) acrylic monomer units. The higher the content of the (meth) acrylic monomer unit, the higher the curability tends to be.

The (meth) acryloyl equivalent of the component A varies depending on the structure of the main chain, the weight average molecular weight, etc., but is preferably in the range of 100 to 10,000 g / mol, more preferably in the range of 400 to 8000 g / mol. It is more preferably in the range of 750 to 5000 g / mol. The larger the (meth) acryloyl equivalent, the smaller the shrinkage stress generated during curing, and the better the adhesion. Further, the smaller the (meth) acryloyl equivalent, the better the curability.

The weight average molecular weight (Mw) of component A needs to be 1000 or more and 20000 or less. By setting the weight average molecular weight within this range, the miscibility with the diluent becomes good and the preparation of the present composition becomes easy. Further, when used as a UV ink, it has high curability, and the cured product has preferable effects of high strength, low odor, and high adhesion.

The weight average molecular weight of the component A is preferably 1000 or more and 10000 or less, more preferably 1000 or more and 7000 or less, and further preferably 1000 or more and 4900 or less. The larger the weight average molecular weight, the smaller the shrinkage stress generated during UV curing, so the adhesion tends to improve. On the other hand, the smaller the weight average molecular weight, the lower the resin viscosity, which tends to improve the coating workability.

The weight average molecular weight of component A can be determined by appropriately controlling the polymerization conditions when polymerizing the raw material monomer, for example, the type and amount of the polymerization initiator, the type and amount of the solvent, the reaction temperature, the reaction time, and the like. It can be adjusted within the above range. In the present specification, the term "weight average molecular weight" means a polystyrene-equivalent weight average molecular weight measured by a GPC-LS method (GelPermeation Chromatography-Light Scattering Method: GPC-light scattering method).

The method for introducing the structure of the formula (2) and / or the formula (3) into the component A is not particularly limited, but for example, the (meth) acrylic polymer which is the basic skeleton is chemically modified (meth). ) It can be produced by a method of introducing an acryloyl-based functional group (chemical modification method).

As a method for introducing the structure represented by the formula (2), for example, a (meth) acrylic polymer having an epoxy group is used as a base polymer, and a (meth) acryloyl group and a carboxyl group are added to the epoxy group of the base polymer. Examples thereof include a method of reacting the carboxyl group of the contained compound.

The (meth) acrylic polymer having an epoxy group can be produced, for example, by homopolymerizing glycidyl methacrylate (trade name: Acryester G, manufactured by Mitsubishi Rayon Co., Ltd.) or copolymerizing with another monomer. Examples of the "compound containing (meth) acryloyl group and carboxyl group" include acrylic acid (trade name: acrylic acid, manufactured by Mitsubishi Chemical Co., Ltd.), methacrylic acid (trade name: methacrylic acid, manufactured by Mitsubishi Rayon Co., Ltd.), β. Examples thereof include compounds such as -carboxyethyl acrylate (trade name: β-CEA, manufactured by Daicel Ornex).

Further, as a method for introducing the structure represented by the formula (3), for example, a (meth) acrylic polymer having an isocyanate group is used as a base polymer, and a (meth) acryloyl group and a hydroxyl group are added to the isocyanate group of the base polymer. Examples thereof include a method of reacting the hydroxyl groups of a compound containing.

The (meth) acrylic polymers having an isocyanate group are 2-methacryloyloxyethyl isocyanate (trade name: Karenz MOI, manufactured by Showa Denko) and 2-acryloyloxyethyl isocyanate (trade name: Karenz AOI, manufactured by Showa Denko). It can be produced by homopolymerizing an isocyanate group-containing (meth) acrylate such as the above, or by copolymerizing it with another monomer. Examples of the "compound containing a (meth) acryloyl group and a hydroxyl group" include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate.

Further, as a method for introducing the structure represented by the formula (4) containing a carbon-carbon double bond at one end of the polymer main chain, for example, the chain transfer agent described in International Publication No. 2013/089245. In the presence of the transition metal chelate complex, the (meth) acrylic monomer exemplified as the raw material monomer for introducing the structure represented by the above formula (1) can be produced by radical polymerization. Specific examples of such a chain transfer agent include those obtained by reacting cobalt (II) acetate tetrahydrate with diphenylglycime.

As a method for introducing the structure represented by the formula (5), for example, glycidyl methacrylate is (co) polymerized by the method described in the above-mentioned International Publication No. 2013/089245 to have an epoxy group at the terminal (co). Examples thereof include a method of producing a base polymer of a meta) acrylic polymer and reacting an epoxy group at the end of the base polymer with a carboxyl group of a compound containing a (meth) acryloyl group and a carboxyl group.

As a method for introducing the structure represented by the formula (6), for example, the isocyanate group-containing (meth) acrylate is (co) polymerized by the method described in International Publication No. 2013/089245 to obtain an isocyanate at the terminal. A method of producing a base polymer of a (meth) acrylic polymer having a group and reacting the isocyanate group at the end of the base polymer with a (meth) acryloyl group and a hydroxyl group of a compound containing a hydroxyl group can be mentioned.

Examples of the method for confirming the terminal structure represented by the formulas (4) to (6) include ¹ H-NMR analysis using a nuclear magnetic resonance apparatus. When component A is dissolved in deuterated chloroform and measured by Varian's UNITY INOVA 500 superconducting FT-NMR (trade name), the terminal doubles of formulas (4) to (6) are located near 5.5 and 6.2 ppm. Peaks derived from binding are confirmed.

The content of component A in this product varies depending on the structure of component A, the structure of other monomer units, the type of adherend, the required cured film properties, etc., but the total of all polymerizable components is calculated. When it is set to 100% by mass, it is preferably in the range of 1 to 70% by mass, and more preferably in the range of 5 to 50% by mass. The higher the content, the better the curability and the less the curing shrinkage. Further, the smaller the content, the lower the viscosity and the better the coating workability.

[Photopolymerization initiator (component B)]
If necessary, the composition of the present invention may contain a photopolymerization initiator (hereinafter referred to as component B) for the purpose of improving curability. The component B means an additive having a catalytic action that induces a polymerization reaction by light irradiation when added to the polymerization system. In the present invention, the type thereof is not particularly limited, and conventionally known photopolymerization initiators can be used.

Examples of the B component include benzophenone, α-hydroxyacetophenone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals), α-aminoacetophenone, benzoin compounds and acylphosphine oxide compounds (for example, Irgacure 819 (for example). Photopolymerization initiators such as trade name, Ciba Specialty Chemicals), Lucirin TPO (trade name, BASF), etc. are mentioned. Among them, benzophenone and acylphosphine oxide compounds are selected because of their high reactivity. preferable.

The content of the B component is preferably in the range of 1 to 20 parts by mass, and more preferably in the range of 1 to 10 parts by mass, when the total of all the polymerizable components is 100 parts by mass. If the content is too small, the curability deteriorates and it may not be suitable for UV ink. On the other hand, if the amount is too large, the solvent resistance of the coating film may decrease.

[Monomer having a polymerizable double bond (C component)]
If necessary, the present composition may contain other polymerizable components (hereinafter referred to as “C component”) having a vinyl group other than the A component for the purpose of improving wear resistance and the like. As the C component, a (meth) acryloyl group-containing monomer is preferable. Examples of the (meth) acryloyl group-containing monomer include monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional (meth) acrylate, tetrafunctional or higher (meth) acrylate, and (meth) acrylamide.

Specific examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl acrylate, hexyl acrylate, heptyl (meth) acrylate, and octyl (meth). Meta) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cresol (meth) acrylate , Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, 2-ethylhexyl (Meta) acrylate, ethyldiethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, polyurethane mono (meth) acrylate, polyepoxy mono (meth) acrylate, polyester mono Examples include (meth) acrylate.

Specific examples of the bifunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, and ethylene glycol. Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerol 1,3-di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, tricyclodecanediyl dimethylene di (meth) acrylate, bisphenol A di (meth) acrylate, hydrogenated Bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polycarbonate di (meth) acrylate, or polyalkylene oxide adducts of these monomers, polycaprolactone. Examples thereof include adducts, polycarbonate adducts, polyurethane di (meth) acrylates, polyepoxy di (meth) acrylates, polyester di (meth) acrylates and the like.

Specific examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyurethane tri (meth) acrylate, polyepoxytri (meth) acrylate, and polyester tri (meth) acrylate. And so on.

Specific examples of the tetrafunctional or higher functional (meth) acrylate include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyepoxytetra (meth) acrylate, polyester tetra (meth) acrylate, and dipentaerythritol penta. Penta (meth) acrylates such as (meth) acrylates and tripentaerythritol penta (meth) acrylates; hexa (meth) acrylates such as dipentaerythritol hexa (meth) acrylates and tripentaerythritol hexa (meth) acrylates; Hepta (meth) acrylate such as erythritol hepta (meth) acrylate; octa (meth) acrylate such as tripenta erythritol octa (meth) acrylate; tetrafunctional or higher polyurethane poly (meth) acrylate; tetrafunctional or higher polyepoxy poly ( Meta) acrylate; Examples thereof include tetrafunctional or higher functional polyester poly (meth) acrylate. Further, modified products such as polyalkylene oxide-modified additives, polycaprolactone-modified additives, and polycarbonate-modified additives of the tetrafunctional or higher functional (meth) acrylate monomers, and tetrafunctional or higher functional polyurethane poly (meth). ) Acrylate, polyepoxypoly (meth) acrylate having four or more functionalities, polyester poly (meth) acrylate having four or more functionalities, and the like.

Specific examples of (meth) acrylamide include (meth) acrylamide, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) acrylamide and the like.

One type of C component may be used, or two or more types may be used in combination.
The C component is preferably 30 to 99 parts by mass, more preferably 50 to 95 parts by mass, based on 100 parts by mass of the total amount of the polymerizable component having a vinyl group. The higher the content of the C component, the lower the viscosity, and the better the coating workability. Further, the smaller the content of the C component, the better the curability of the obtained cured film.

As a method of blending the C component into the present composition, for example, when chemically modifying the A component (bonding a (meth) acrylic compound having a carboxyl group to an epoxy group, etc.), it may be blended in advance as a diluting component. Alternatively, it may be blended after chemical modification.

[UV ink]
When this composition is used as a UV ink, it may contain pigments and dyes.
Specific examples of pigments include Carmin 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmin FB, Chromophthal Yellow, Chromophtal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenda, and Quinacridone Red. , Industron Blue, Pyrimidine Yellow, Thioingio Bordeaux, Thioing Digo Magenta, Perylene Red, Perinon Orange, Isodolinone Yellow, Aniline Black, Daylight Fluorescent Pigments and other organic pigments, Carbon Black, Aluminum Powder, Bronze Powder Examples thereof include inorganic pigments such as chrome vermillion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, navy blue, red iron oxide, yellow iron oxide, iron black, titanium oxide, and zinc oxide.

Specific examples of the dye include tartrazine lake, rodolin 6G lake, Victoria pure blue lake, alkaline blue G toner, brilliant green lake and the like.

The pigments and dyes are preferably blended in the range of 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by mass of the total amount of the polymerizable component having a vinyl group. The higher the content of the pigment or dye, the lower the viscosity and the better the coating workability. Further, the smaller the content of the pigment or dye, the better the curability of the obtained cured film.

(Other ingredients)
The composition contains sensitizers, dispersants, waxes, light stabilizers, antioxidants, surface conditioners, defoamers, heat stabilizers, antistatic agents, antifogging agents, resins, and fine particles, as required. , Thixotropic agents, coupling agents, and other components such as organic solvents can be included.

Specific examples of the sensitizer include benzoin isopropyl ether and thioxanthone.

Specific examples of the dispersant include Anti-Terra-U, Anti-Terra-203 / 204, Disperbyk-101, 107, 110, 111, 130, 161, 162, 163, 164, 165, 166 manufactured by BYK Chemie. , 170, 400, Bykumen, BYK-P104, P105, P104S, 240S, Lactimon (all of which are trade names).

Specific examples of the wax include polyamide wax and polyethylene oxide wax.

Specific examples of the light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. Examples thereof include hindered amines such as 1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate.

Specific examples of the antioxidant include hindered phenol compounds, organic phosphite compounds and organic phosphonite compounds.

Specific examples of surface conditioners and defoamers include non-silicone defoamers such as polysiloxane, polysiloxane defoamers such as fluorine-modified polysiloxane, and copolymers of alkyl methacrylate, polyacrylate, and acrylic acid. Examples thereof include acrylic acid-based defoamers, butadiene copolymer-based defoamers, and mineral oil-based defoamers.

Specific examples of the heat stabilizer include triphenylphosphine, tris (2,6-dimethylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, and tris (mono-nonylphenyl) phos. Mixtures of phyto and tris (di-nonylphenyl) phosphine, dimethylbenzenephosphonate and trimethylphosphate can be mentioned.

Specific examples of the antistatic agent include glycerol monostearate, sodium stearyl sulfonate and sodium dodecylbenzene sulfonate.

Specific examples of the antifogging agent include glycerol-1-methacryloyloxyethyl urethane and glycerol-1-methacryloyloxypropyl urethane.

Specific examples of the resin include acrylic resin, acrylonitrile resin, butadiene resin, urethane resin, polyester resin, polyamide resin, polyamideimide resin and phenol resin.

Specific examples of the fine particles include organic fillers such as acrylic beads and urethane beads, inorganic fillers such as silica and titanium, and inorganic fillers whose surface has been organically treated with a silane coupling agent or the like. Examples of the method of blending these into the present composition include a method of blending those in a pre-dispersed state and a method of blending the fine particles in the present composition and then dispersing them using a triple roll, a dyno mill or the like. .. Further, in order to improve the dispersibility, a dispersant such as a carboxylic acid type, a polycarboxylic acid type or a polyacrylic acid type can be used.

Specific examples of the thixotropic agent include organic thixotropic agents such as amide, polyethylene oxide, and hydrogenated castor oil, silica, bentonite, organic silane coupling products thereof, and inorganic compounds such as surface-treated calcium carbonate. Examples include thixotropic agents.

Specific examples of the coupling agent include a silane coupling agent to which a functional group such as a (meth) acryloyloxy group, a vinyl group, an epoxy group and an amino group is added, and a titanium coupling agent.

Specific examples of the organic solvent include hydrocarbon solvents such as n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane, aromatic solvents such as toluene, xylene and ethylbenzene, methanol, ethanol and n-butanol. Alcohol-based solvents such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, ester solvents such as ethyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone and methyl. Ketone solvents such as isobutyl ketone, methyl n-amyl ketone and cyclohexanone, ethylene glycol solvents such as diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, N-methylpyrrolidone and dimethyl Examples thereof include amide solvents such as formamide and dimethylacetamide and carbonate solvents such as ethylene carbonate. The content of the solvent is preferably 30 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of the polymerizable component having a vinyl group. The larger the solvent content, the higher the viscosity of the resin composition. It becomes lower and the painting workability and leveling performance are improved. Further, the smaller the solvent content, the lower the VOC emission amount.

[Base material]
This composition can be used for decorating the surface of paper as a base material and various resin molded products. Specific examples of resin molded products include polymethylmethacrylate resin, polycarbonate resin, polyester resin, polyester carbonate resin, polystyrene resin, acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene resin, polyamide resin, polyarylate resin, and polymethacrylicimide resin. , Polyallyl diglycol carbonate resin and the like. In particular, polymethylmethacrylate resin, polycarbonate resin, polystyrene resin, and polymethacrylicimide resin are excellent in transparency and have strong demand for improvement in abrasion resistance, so that it is very effective to apply this composition. The resin molded product is a molded product having various shapes such as a sheet-shaped molded product, a film-shaped molded product, and various injection-molded products made of these resins.
The thickness of the base material is preferably 0.001 to 10 mm, more preferably 0.01 to 5 mm from the viewpoint of rigidity.

[Painting method]
By applying this composition to the surface of a base material and irradiating the obtained coating film with active energy rays, a cured film having excellent wear resistance and weather resistance can be formed on the surface of the base material. .. In order to apply the composition to the substrate, for example, a method such as brush coating, spray coating, dip coating, spin coating, curtain coating, bar coating and the like can be used. Further, the composition may be heated or diluted with a subcritical fluid before coating in order to adjust the viscosity. The thickness of the coating film of the present composition is preferably 0.001 mm or more and 0.05 mm or less, more preferably 0.002 mm or more and 0.03 mm or less, from the viewpoint of curability and abrasion resistance of the present composition. It is preferable, and more preferably 0.004 mm or more and 0.02 mm or less.

[Curing method]
When the coating film of the present composition is irradiated with active energy rays, it is cured to form a cured film. Examples of the active energy rays used include α rays, β rays, γ rays, and ultraviolet rays. From the viewpoint of versatility, ultraviolet rays are preferable as the active energy rays. Examples of the ultraviolet source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless UV lamp using a magnetron, and an LED.

Examples of the atmosphere for curing the coating film include an inert gas such as air, nitrogen, and argon. From the viewpoint of practicality and economy, air is preferable as the atmosphere. As a preferable curing condition when ultraviolet rays are used as the active energy rays, for example, it is preferable to irradiate with a high-pressure mercury lamp so that the integrated light amount at a wavelength of 340 to 380 nm is 10 to 3000 mJ / cm ² .

Hereinafter, the present invention will be described with reference to examples. In the following description, "part" means a mass part.

[Production Example 1] Production of Dispersant A 900 parts by mass of deionized water, 60 parts by mass of 2-sulfoethyl sodium methacrylate, 10 parts by mass of potassium methacrylate and methacrylic acid in a flask equipped with a stirrer, a cooling tube and a thermometer. 12 parts by mass of methyl acetate was added and stirred, and the temperature was raised to 50 ° C. while substituting nitrogen in the flask. Next, 0.08 parts by mass of 2,2'-azobis (2-methylpropionamidine) dihydrochloride salt as a polymerization initiator was added to the flask, and the temperature was further raised to 60 ° C. After the temperature was raised, 18 parts by mass of methyl methacrylate was continuously added dropwise at a rate of 0.24 parts by mass / min using a dropping pump. The obtained reaction solution was held at 60 ° C. for 6 hours and then cooled to room temperature to obtain a clear aqueous solution of a dispersant having a solid content of 10% by mass (hereinafter referred to as dispersant A).

[Production Example 2] Production of chain transfer agent A In a flask equipped with a stirrer, 1.00 g of cobalt (II) acetate tetrahydrate, 1.93 g of diphenylglioxime and nitrogen bubbling are previously removed under a nitrogen atmosphere. 80 ml of oxygenated diethyl ether was added and stirred at room temperature for 30 minutes. Then, 10 ml of boron trifluoride diethyl ether complex was added, and the mixture was further stirred for 6 hours. The obtained reaction product was filtered, the solid content was washed with diethyl ether, and the mixture was vacuum dried for 15 hours to obtain 2.12 g of a chain transfer agent (hereinafter referred to as chain transfer agent A) as a reddish brown solid.

[Production Example 3] Production of acrylic polymer (P1) In a flask equipped with a stirrer, a cooling tube and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate and 0.25 part of dispersant A are placed. The mixture was stirred to obtain a uniform aqueous solution. Next, 79.95 parts of methyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acryester M), 0.05 part of ethyl acrylate (manufactured by Mitsubishi Chemical Co., Ltd., trade name: ethyl acrylate), glycidyl methacrylate (Mitsubishi). Made by Rayon Co., Ltd., trade name: Acryester G) 20 parts, chain transfer agent A 0.005 parts and 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoate (manufactured by Nichiyu Co., Ltd.) , Trade name: Perocta O) 1.33 parts of a monomer mixture was added to prepare an aqueous suspension. After that, the inside of the flask was replaced with nitrogen, the temperature was raised to 80 ° C. and reacted for 3 hours, and the temperature was raised to 93 ° C. and held for 1 hour in order to further increase the polymerization rate. Then, the reaction solution was cooled to 40 ° C. to obtain an aqueous polymer suspension. This aqueous polymer suspension is filtered through a nylon filter cloth having an opening of 45 μm, the filter medium is washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain an acrylic polymer (hereinafter referred to as P1). Got The weight average molecular weight (hereinafter referred to as Mw) of P1 by GPC (Gel Permeation Chromatography) was measured using a GPC system (manufactured by Toso Co., Ltd., trade name: HLC-8220GPC) under the following conditions. As a result, Mw was 3100.

(GPC measurement conditions)
Columns: "TSK-gel superHZM-M", "TSK-gel HZM-M", "TSK-gel HZ2000";
Eluent: THF;
Flow rate: 0.35 ml / min;
Injection volume: 10 μl;
Column temperature: 40 ° C;
Detector: UV-8020.

Further, P1 has a structure in the formula (1) in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group, R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. It has a structure in which R ¹ is a methyl group or a glycidyl group in the formula (4), and does not have the structures of the formulas (2), (3), (5) and (6).

[Production Example 4] Production of Acrylic Polymer (P2) Except that the chain transfer agent A was 0.0023 parts and 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoate was 0.8 parts. Produced an acrylic polymer (hereinafter referred to as P2) in the same manner as in Production Example 3. The Mw measured in the same manner as in Production Example 3 was 7100. Further, in the formula (1), P2 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. It has a structure in which R ¹ is a methyl group or a glycidyl group in the formula (4), and does not have the structures of the formulas (2), (3), (5) and (6).

[Production Example 5] Production of Acrylic Polymer (P3) An acrylic polymer (hereinafter referred to as P3) was produced in the same manner as in Production Example 3 except that the chain transfer agent A was 0.0035 parts. The Mw measured in the same manner as in Production Example 3 was 4300. Further, P3 has a structure in the formula (1) in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. It has a structure in which R ¹ is a methyl group or a glycidyl group in the formula (4), and does not have the structures of the formulas (2), (3), (5) and (6).

[Production Example 6] Production of Acrylic Polymer (P4) An acrylic polymer (hereinafter referred to as P4) was produced in the same manner as in Production Example 3 except that the amount of methyl methacrylate was 59.95 parts and the amount of glycidyl methacrylate was 40 parts. The Mw measured in the same manner as in Production Example 3 was 3800. Further, in the formula (1), P4 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. It has a structure in which R ¹ is a methyl group or a glycidyl group in the formula (4), and does not have the structures of the formulas (2), (3), (5) and (6).

[Production Example 7] Production of Acrylic Polymer (P5) An acrylic polymer (hereinafter referred to as P5) was produced in the same manner as in Production Example 3 except that 97.95 parts of methyl methacrylate and 2 parts of glycidyl methacrylate were used. The Mw measured in the same manner as in Production Example 3 was 2900. Further, P5 has a structure in the formula (1) in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. It has a structure in which R ¹ is a methyl group or a glycidyl group in the formula (4), and does not have the structures of the formulas (2), (3), (5) and (6).

[Production Example 8] Production of Acrylic Polymer (P6) Except for the addition of 89.95 parts of methyl methacrylate, 0 parts of glycidyl methacrylate, 0.0035 parts of chain transfer agent A, and 10 parts of 2-hydroxyethyl methacrylate. An acrylic polymer (hereinafter referred to as P6) was produced in the same manner as in Production Example 3. The Mw measured in the same manner as in Production Example 3 was 3500. In P6, in the formula (1), R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a 2-hydroxyl ethyl group and R ² is a methyl group. It has a certain structure, and in the formula (4), R ¹ has a structure of a methyl group or a 2-hydroxyl ethyl group, and the structures of the formulas (2), (3), (5) and (6) are present. Not done.

[Production Example 9] Production of Acrylic Polymer (P7) 30 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) and 26.7 parts of butyl acetate are placed in a flask equipped with a stirrer, a cooling tube and a thermometer and stirred. And a uniform solvent was used. Next, the inside of the flask was replaced with nitrogen and the temperature was raised to 110 ° C., 20 parts of styrene (manufactured by Nippon Steel & Sumitomo Metal Corporation, trade name: styrene monomer), 2-ethylhexyl acrylate (manufactured by Mitsubishi Chemical Co., Ltd., trade name: acrylic). 21 parts of 2-ethylhexyl acid, 2-ethylhexyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: acrylic ester EH) 23.2 parts, 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: acrylic ester) HO) 34.8 parts, methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd., trade name: methacrylic acid) 1 part, 2,2'-azobis (2-methylbutyronitrile) (manufactured by Otsuka Chemical Co., Ltd., trade name) : A mixed solution of 2.5 parts of AMBN) and 2.4 parts of t-butylperoxy-2-ethylhexanoate (manufactured by Nichiyu Co., Ltd., trade name: Perocta O) was added dropwise over 3 hours. After another 1 hour, in order to increase the polymerization rate, a mixed solution of 0.2 parts of 2,2'-azobis (2-methylbutyronitrile) and 10 parts of MIBK was added and held for 2 hours. Then, the reaction solution was cooled to 40 ° C., and MIBK and butyl acetate were volatilized to produce an acrylic polymer (hereinafter referred to as P7). The Mw measured in the same manner as in Production Example 3 was 9000. In P7, in the formula (1), R ¹ is a 2-ethylhexyl group and R ² is hydrogen, R ¹ is a 2-ethylhexyl group and R ² is a methyl group, and R ¹ is a 2-hydroxyl ethyl group and R ^2. Has a structure in which is a methyl group, and does not have the structures of the formulas (2), (3), (4), (5) and (6).

[Production Example 10] Production of Acrylic Polymer (P8) An acrylic polymer (hereinafter referred to as P8) was produced in the same manner as in Production Example 3 except that the chain transfer agent was 0 parts. The Mw measured in the same manner as in Production Example 3 was 23000. Further, in the formula (1), P8 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. It has, and does not have the structures of the formulas (2), (3), (4), (5) and (6).

[Production Example 11] Synthesis of polymer (A1) having a (meth) acryloyl group in the side chain 1,6-hexanediol diacrylate in a 5-liter four-necked flask equipped with a stirrer, a cooling tube and a thermometer. (Manufactured by MIWON, trade name: Miramar M200) 100 parts were added and the temperature was raised to 70 ° C. in 1 hour. Subsequently, 90.79 parts of the acrylic polymer P1 synthesized in Production Example 3, 9.21 parts of acrylic acid (manufactured by Mitsubishi Chemical Co., Ltd., trade name: acrylic acid), triphenylphosphine (Wako Pure Chemical Industries, Ltd.) (Manufactured by) 0.33 parts, hydroquinone monomethyl ether (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name: MQ) 0.1 parts were added. The mixture was heated to 97 ° C. for 3 hours and then held for 10 hours to obtain a polymer (A1) having a (meth) acryloyl group dissolved in 1,6-hexanediol diacrylate. The Mw of A1 was calculated to be 3500 by excluding the components having a molecular weight of 1000 or less. Further, in the formula (1), A1 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group, R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. In the formula (2), n = 0, R ²¹ is a methyl group and R ²² is hydrogen, and in the formula (4), R ¹ is a methyl group or a glycidyl group. , In the formula (5), it has a structure in which R ² is hydrogen, and does not have the structures of the formulas (3) and (6).

[Production Example 12] Synthesis of Polymer (A2) Having (Meta) Acryloyl Group in Side Chain Acrylic polymer (meth) acryloyl group is used in the same manner as in Production Example 11 except that the acrylic polymer P1 is the acrylic polymer P2. A polymer (A2) having was produced. The Mw of A2 was calculated to be 7800 by excluding the components having a molecular weight of 1000 or less. Further, in the formula (1), A2 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. In the formula (2), n = 0, R ²¹ is a methyl group and R ²² is hydrogen, and in the formula (4), R ¹ is a methyl group or a glycidyl group. in equation (5), n = 0, R 2 has the structure which is hydrogen, the structure of formula (3) and (6) does not.

[Production Example 13] Synthesis of Polymer (A3) Having (Meta) Acryloyl Group in Side Chain A polymer having (meth) acryloyl group as in Production Example 11 except that the acrylic polymer P1 is the acrylic polymer P3. (A3) was manufactured. The Mw of A3 was calculated to be 4800 by excluding the components having a molecular weight of 1000 or less. Further, in the formula (1), A3 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. In the formula (2), n = 0, R ²¹ is a methyl group and R ²² is hydrogen, and in the formula (4), R ¹ is a methyl group or a glycidyl group. in equation (5), n = 0, R 2 has the structure which is hydrogen, the structure of formula (3) and (6) does not.

[Production Example 14] Synthesis of Polymer (A4) Having (Meta) Acryloyl Group in Side Chain 90.79 parts of acrylic polymer P1 is changed to 83.14 parts of acrylic polymer P4, and the amount of acrylic acid is 16. A polymer (A4) having a (meth) acryloyl group was produced in the same manner as in Production Example 11 except that the number was 86 parts. The Mw of A4 was calculated to be 4600 by excluding the components having a molecular weight of 1000 or less. Further, in the formula (1), A4 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. In the formula (2), n = 0, R ²¹ is a methyl group and R ²² is hydrogen, and in the formula (4), R ¹ is a methyl group or a glycidyl group. in equation (5), n = 0, R 2 has the structure which is hydrogen, the structure of formula (3) and (6) does not.

[Production Example 15] Synthesis of polymer (A5) having (meth) acryloyl group in the side chain 90.79 parts of acrylic polymer P1 is changed to 99.00 parts of acrylic polymer P5, and the amount of acrylic acid is 1. A polymer (A5) having a (meth) acryloyl group was produced in the same manner as in Production Example 11 except that the number was 00 parts. The Mw of A5 was calculated to be 3000 by excluding the components having a molecular weight of 1000 or less. Further, in the formula (1), A5 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. In the formula (2), n = 0, R ²¹ is a methyl group and R ²² is hydrogen, and in the formula (4), R ¹ is a methyl group or a glycidyl group. in equation (5), n = 0, R 2 has the structure which is hydrogen, the structure of formula (3) and (6) does not.

[Production Example 16] Synthesis of Polymer (A6) Having (Meta) Acryloyl Group in Side Chain 90.79 parts of acrylic polymer P1 is changed to 90.22 parts of acrylic polymer P6, and 9.21 parts of acrylic acid is used. A polymer (A6) having a (meth) acryloyl group was produced in the same manner as in Production Example 11 except that 9.78 parts of acryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., trade name: Karens AOI) was used. The Mw of A6 was calculated to be 4100 by excluding the components having a molecular weight of 1000 or less. In A6, in the formula (1), R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a 2-hydroxyl ethyl group and R ² is a methyl group. It has a structure in which R ³¹ is an ethylene group, R ³² is an ethylene group and R ² is hydrogen in the formula (3), and in the formula (4), R ¹ is a methyl group or 2-hydroxyl. It has a structure of an ethyl group, and in the formula (6), it has a structure in which R ³¹ is an ethylene group, R ³² is an ethylene group, and R ² is hydrogen, and the structures of the formulas (2) and (4) are present. Not done.

[Production Example 17] Synthesis of polymer (A7) having a (meth) acryloyl group in the side chain Except that the 1,6-hexanediol diacrylate was dipentaerythritol hexaacrylate (manufactured by MIWON, trade name: Miramar M600). A polymer (A7) having a (meth) acryloyl group was produced in the same manner as in Production Example 11. The Mw of A7 was calculated to be 3500 by excluding the components having a molecular weight of 1000 or less. Further, in the formula (1), A7 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. In the formula (2), n = 0, R ²¹ is a methyl group and R ²² is hydrogen, and in the formula (4), R ¹ is a methyl group or a glycidyl group. in equation (5), n = 0, R 2 has the structure which is hydrogen, the structure of formula (3) and (6) does not.

[Production Example 18] Synthesis of polymer (A8) having a (meth) acryloyl group in the side chain Except that the 1,6-hexanediol diacrylate was dipentaerythritol hexaacrylate (manufactured by MIWON, trade name: Miramar M600). A polymer (A8) having a (meth) acryloyl group was produced in the same manner as in Production Example 12. The Mw of A8 was calculated to be 7800 by excluding the components having a molecular weight of 1000 or less. Further, in the formula (1), A8 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. In the formula (2), n = 0, R ²¹ is a methyl group and R ²² is hydrogen, and in the formula (4), R ¹ is a methyl group or a glycidyl group. in equation (5), n = 0, R 2 has the structure which is hydrogen, the structure of formula (3) and (6) does not.

[Production Example 19] Synthesis of polymer (A9) having a (meth) acryloyl group in the side chain In a flask equipped with a stirrer, a cooling tube and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate and 0.25 part of the dispersant A was added and stirred to obtain a uniform aqueous solution. Next, 79.95 parts of methyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acryester M), 0.05 part of ethyl acrylate (manufactured by Mitsubishi Chemical Co., Ltd., trade name: ethyl acrylate), glycidyl methacrylate (Mitsubishi). Made by Rayon Co., Ltd., trade name: Acryester G) 20 parts, chain transfer agent A 0.005 parts and 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoate (manufactured by Nichiyu Co., Ltd.) , Trade name: Perocta O) 1.33 parts of a monomer mixture was added to prepare an aqueous suspension. After that, the inside of the flask was replaced with nitrogen, the temperature was raised to 80 ° C. and reacted for 3 hours, and the temperature was raised to 93 ° C. and held for 1 hour in order to further increase the polymerization rate. After that, the reaction solution was cooled to 40 ° C., the inside of the flask was replaced with air from nitrogen, and β-carboxyethyl acrylate (manufactured by Daicel Ornex Co., Ltd., trade name: β-CEA) 20.26 parts, triethylammonium. 2.5 parts of Chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.1 parts of hydroquinone monomethyl ether (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name: MQ) were added. The mixture was heated to 95 ° C. for 1 hour and then held for 10 hours to obtain an aqueous polymer suspension. The aqueous polymer suspension was filtered through a nylon filter cloth with an opening of 45 μm, the filter was washed with deionized water, dehydrated, dried at 40 ° C. for 16 hours, and the (meth) acryloyl group was added to the side chain. A polymer having the same (hereinafter referred to as A9) was obtained. The Mw of A9 was calculated to be 3300 by excluding the components having a molecular weight of 1000 or less. Further, in the formula (1), A9 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. It has a structure in which n = 1, R ²¹ is a methyl group and R ²² is hydrogen in the formula (2), and has a structure in which R ¹ is a methyl group or a glycidyl group in the formula (4). , In the formula (5), it has a structure in which n = 1 and R ² are hydrogen, and does not have the structures of the formulas (3) and (6).

[Production Example 20] Synthesis of polymer (X1) having (meth) acryloyl group in the side chain 83.84 parts of acrylic polymer P7 in a flask equipped with a stirrer, a cooling tube, a thermometer and a water separator. 16.16 parts of acrylic acid, 100 parts of toluene, 2 parts of p-toluenesulfonic acid and 0.05 part of hydroquinone were charged, and the mixture was heated and stirred to reflux the toluene, and the reaction was continued until no water formation was observed. It was volatilized to produce a polymer (X1) having a (meth) acryloyl group. The Mw of X1 was 11000. Further, in the formula (1), X1 is R ¹ being a 2-ethylhexyl group and R ² being hydrogen, R ¹ being a 2-ethylhexyl group and R ² being a methyl group, and R ¹ being a 2-hydroxyl ethyl group and being R ^2. Has a structure in which is a methyl group, and does not have the structures of the formulas (2), (3), (4), (5) and (6).

[Production Example 21] Synthesis of Polymer (X2) Having (Meta) Acryloyl Group in Side Chain A polymer having an acrylic polymer (meth) acryloyl group (meth) as in Production Example 11 except that the acrylic polymer is P8. X2) was manufactured. The Mw of X2 was calculated by cutting a component having a molecular weight of 1000 or less and found to be 25,000. Further, in the formula (1), X2 has a structure in which R ¹ is a methyl group, R ² is a methyl group, R ¹ is an ethyl group and R ² is hydrogen, and R ¹ is a glycidyl group and R ² is a methyl group. In formula (2), n = 0, R ²¹ is a methyl group and R ²² is hydrogen, and the structures of formulas (3), (4), (5) and (6) are present. Not done.

Table 1 shows the presence or absence of the structures represented by the formulas (1) to (6) and the weight average molecular weight contained in each of the polymers produced in Production Examples 1 to 21.

[Example 1]
(1) Preparation of active energy ray-polymerizable composition and E-type viscosity An active energy ray-polymerizable composition prepared with the compounding ratio shown in Table 2 is used as a viscometer manufactured by Toki Sangyo Co., Ltd. (trade name: VISCOMETER TVE). -20H) was used to measure the 50 ° C. E-type viscosity of the resin composition. The evaluation results are shown in Table 2.

(Evaluation criteria for E-type viscosity)
A: E-type viscosity is less than 50,000 mPa ・ s F: E-type viscosity is 50,000 mPa ・ s or more

(2) Coating method of active energy ray-polymerizable composition A bar of the active energy ray-polymerizable composition prepared in the blending ratio shown in Table 2 is placed on a glass plate having a thickness of 2 mm so that the thickness of the cured film is 10 μm. The coat was painted.

(3) Evaluation of Curability of Coating Film Using a high-pressure mercury lamp in air on the dried coating film obtained in (2), the peak illuminance at a wavelength of 300 nm to 400 nm is 80 mW / cm ² , and the integrated light intensity is 100 mJ. / cm ² of ultraviolet irradiation, lightly touched with a fingertip, to confirm whether the tack-free. If it was not tack-free, this ultraviolet irradiation step was repeated until it became tack-free. Curability was evaluated according to the following criteria based on the required integrated light intensity. The evaluation results are shown in Table 2.

(Evaluation criteria for curability)
A: Required integrated light amount is less than 2700 mJ / cm ² B: Required integrated light amount is 2700 mJ / cm ² or more and less than 3700 mJ / cm ² F: Required integrated light amount is 3700 mJ / cm ² or more

(4) Evaluation of Curing Shrinkage Rate of Cured Film Using the liquid specific gravity of the resin composition prepared at the compounding ratio shown in Table 2 and a high-pressure mercury lamp in the air, the peak illuminance at a wavelength of 300 nm to 400 nm is 80 mW / cm ² The curing shrinkage rate was calculated from the ratio of the specific gravities of those cured by irradiating ultraviolet rays having an integrated light amount of 5000 mJ / cm ² using the following formula.
Curing shrinkage rate (%) = (cured product specific gravity-liquid specific gravity) / cured product specific gravity x 100
(Evaluation criteria for curing shrinkage rate)
A: Curing shrinkage rate is less than 7% B: Curing shrinkage rate is 7% or more and less than 8% F: Curing shrinkage rate is 8% or more

[Examples 2 to 8 and Comparative Examples 1 to 4]
An active energy ray-polymerizable composition was prepared in the same manner as in Example 1 except that the composition of the active energy ray-polymerizable composition was changed to the composition shown in Table 2, and a resin molded product with a cured film was prepared using the active energy ray-polymerizable composition. It was prepared and evaluated. The evaluation results are shown in Table 2.
The abbreviations in Table 2 are as follows: ・ "P1": Polymer synthesized in Production Example 3 (P1)
-"P2": Polymer (P2) synthesized in Production Example 4
-"P3": Polymer (P3) synthesized in Production Example 5
-"P4": Polymer (P4) synthesized in Production Example 6
-"P5": Polymer (P5) synthesized in Production Example 7
-"P6": Polymer (P6) synthesized in Production Example 8
-"P7": Polymer (P7) synthesized in Production Example 9
-"P8": Polymer (P8) synthesized in Production Example 10
-"A1": Polymer (A1) synthesized in Production Example 11
-"A2": Polymer (A2) synthesized in Production Example 12
-"A3": Polymer (A3) synthesized in Production Example 13
-"A4": Polymer (A4) synthesized in Production Example 14
-"A5": Polymer (A5) synthesized in Production Example 15
-"A6": Polymer (A6) synthesized in Production Example 16.
-"A7": Polymer (A7) synthesized in Production Example 17
-"A8": Polymer (A8) synthesized in Production Example 18
-"A9": Polymer (A9) synthesized in Production Example 19
"X1": Polymer (X1) synthesized in Production Example 20
"X2": Polymer (X2) synthesized in Production Example 21
-"BNP": Benzophenone (manufactured by Daido Kasei Kogyo Co., Ltd., product name: BENZOPHENONE)
-"TPO": 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF, trade name: Lucillin TPO)
-"HDDA": 1,6-hexanediol diacrylate (manufactured by MIWON, trade name: Miramar M200)
-"DPHA": Dipentaerythritol hexaacrylate (manufactured by MIWON, product name: Miramar M600)
-"TiO ₂ ": Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., product name: CR-97)

In Production Examples 1 to 6 and Production Examples 11 to 19, since the solvent removing step was not included, the component A could be produced at low cost. Further, from the evaluation results shown in Table 2, it was found that the active energy ray-polymerizable composition of the example containing the component A was a good composition having a low viscosity, excellent curability, and less curing shrinkage. ..

On the other hand, the active energy ray-polymerizable compositions of Comparative Examples 1 to 4 containing no component A did not satisfy all of curing shrinkage, viscosity, and curability.

Claims (8)

It contains at least one structure selected from the structures represented by the formulas (2) and (3) and the structure represented by the formula (1), and one end of the polymer main chain is represented by the formulas (4), (5) and. A UV ink having one structure selected from the formula (6) and comprising an active energy ray-polymerizable composition containing a polymer (A) having a weight average molecular weight of 1000 or more and 20000 or less.
In the structures represented by the formulas (1) to (6) , R ¹ represents any of a substituted or unsubstituted alkyl group, cycloalkyl group and aryl group, and R ² , R ²¹ and R ²² are independently hydrogen. or a methyl group, R ³¹ and R ³² represents any their respective independently represent a substituted or unsubstituted alkylene, cycloalkylene and arylene groups. The substituent of R ¹ is any of an epoxy group, a hydroxy group, a cyano group, an isocyanate group, an amino group and a carboxyl group, and the substituents of R ³¹ and R ³² are an epoxy group, a hydroxy group, a cyano group and an isocyanate. It is either a group, an amino group or a carboxyl group. Further, n = 0 to 2. The UV ink comprising the active energy ray-polymerizable composition according to claim 1, wherein the polymer (A) has a weight average molecular weight of 1000 or more and 4900 or less. The UV ink comprising the active energy ray-polymerizable composition according to claim 1 or 2, wherein the (meth) acryloyl equivalent of the polymer (A) is 750 g / eq or more. The UV ink comprising the active energy ray-polymerizable composition according to any one of claims 1 to 3, wherein the polymer (A) is a polymer containing the structure of the formula (2). The polymer (A) is contained in an amount of 1 to 70% by mass and the monomer (C) having a polymerizable double bond is contained in an amount of 30 to 99% by mass, and the photopolymerization initiator (B) is added to 100 parts by mass of the polymerizable component. A UV ink comprising the active energy ray-polymerizable composition according to any one of claims 1 to 4, which contains 1 to 20 parts by mass. The UV ink comprising the active energy ray-polymerizable composition according to any one of claims 1 to 5, wherein the solvent is 5 parts by mass or less with respect to 100 parts by mass of the polymerizable component. A polymer containing a glycidyl (meth) acrylate unit and / or a hydroxyl group-containing (meth) acrylate unit is dissolved in a monomer (C) having a polymerizable double bond, and the epoxy group and / or hydroxyl of the polymer is dissolved. The active energy ray-polymerizable composition according to any one of claims 1 to 6, which comprises a step of producing the polymer (A) by adding a compound containing a (meth) acryloyl group and a carboxyl group to the group. A method for producing UV ink made of materials. A step of producing the polymer (A) by dispersing a polymer containing a glycidyl (meth) acrylate unit in water and adding a compound containing a (meth) acryloyl group and a carboxyl group to the epoxy group of the polymer. A method for producing a UV ink comprising the active energy ray-polymerizable composition according to any one of claims 1 to 6.