JP2011208026A - Active energy ray-curable resin composition and coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition that has excellent adhesion to a metal substrate such as aluminum, SUS or the like and produces a cured film hardly causing the peeling and appearance change of the film under severe conditions such as during boiling of the coated metal substrate.SOLUTION: The active energy ray-curable resin composition includes (A) a urethane (meth)acrylate compound produced by reacting (a1) a hydroxyl group-containing (meth)acrylate compound, (a2) a polyisocyanate compound and (a3) a polyol compound, (B) a urethane (meth)acrylate compound produced by reacting (b1) a hydroxyl group-containing (meth)acrylate compound and (b2) a polyisocyanate compound, (C) an acrylic resin, (D) a polysaccharide derivative and (E) a phosphate group-containing ethylenically unsaturated compound.

Description

  The present invention relates to an active energy ray-curable resin composition and a coating agent, and more particularly, to an active energy ray-curable resin composition for forming a coating layer having excellent adhesion to a metal substrate such as aluminum or SUS. And a coating agent containing the composition.

Conventionally, active energy ray-curable resin compositions are widely used as coating agents, adhesives, anchor coating agents, and the like on various base materials because curing is completed by irradiation of radiation for a very short time.
However, regarding coating agents and paints for forming a cured film on the surface of a metal-based substrate, the coating agents and paints using the active energy ray-curable resin composition are inferior in adhesion to the metal-based substrate. Since it was difficult to obtain a cured film and sufficient adhesion, various developments have been made to improve metal adhesion.
For example, in Patent Document 1, a cured film made of a coating composition containing a phosphate ester having a polymerizable unsaturated group capable of reacting with active energy rays in the molecule as one component of the composition is a metal group. It describes that it has excellent adhesion to the material.
In Patent Document 2, (a) a photocurable acrylate resin, (b) a carboxyl group-containing monofunctional acrylate, (c) a phosphoric acid acrylate, (d) a bifunctional acrylate, (e) a trifunctional or higher functional acrylate, (F) It is described that a photocurable composition comprising a photopolymerization initiator is excellent in curability, and excellent in adhesion to a steel pipe and surface smoothness.

JP 58-219272 A JP 2002-80511 A

  However, in the techniques disclosed in Patent Documents 1 and 2, adhesion to a metal substrate is recognized to some extent by using a phosphate ester, but it cannot be said that it is sufficient in consideration of application conditions (environment) of the metal substrate. . For example, metal substrates are often exposed to high-temperature and high-humidity conditions such as boiling at the time of processing and production. Taking these into account, they are excellent in coating performance under severe conditions and mechanical as a coating agent. There has been a demand for the development of an active energy ray-curable resin composition having excellent physical properties.

  Therefore, the present invention is excellent in adhesion to metal substrates such as aluminum and SUS under such a background, and further, the coating film can be used under severe conditions such as boiling of the coated metal substrate. It is an object of the present invention to provide an active energy ray-curable resin composition and a coating agent that can provide a cured film that hardly undergoes peeling or appearance change.

  However, as a result of intensive studies in view of such circumstances, the present inventor has obtained an active energy ray-curable resin composition containing a urethane (meth) acrylate compound, an acrylic resin, and a phosphoric acid group-containing ethylenically unsaturated compound. As a urethane (meth) acrylate compound, a urethane (meth) acrylate compound having a structural moiety derived from a polyol component and a urethane (meth) acrylate compound not having a structural moiety derived from a polyol component are used in combination, It has been found that by containing a polysaccharide derivative, a cured film is obtained in which peeling of the film and change in appearance hardly occur even under severe conditions such as boiling, and the present invention has been completed.

That is, the present invention provides a urethane (meth) acrylate compound (A) obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a1), a polyvalent isocyanate compound (a2), a polyol compound (a3), a hydroxyl group. Urethane (meth) acrylate compound (B), acrylic resin (C), polysaccharide derivative (D), and phosphorus obtained by reacting the (meth) acrylate compound (b1), polyvalent isocyanate compound (b2) An active energy ray-curable resin composition comprising an acid group-containing ethylenically unsaturated compound (E) is provided.
Moreover, in this invention, the coating agent containing the said active energy ray hardening-type resin composition, especially the coating agent for metal substrates are also provided.

  The active energy ray-curable resin composition of the present invention exhibits excellent adhesion to a metal substrate, and even when applied to a metal substrate with a relatively thick film thickness, the adhesion is impaired. Furthermore, it has an excellent effect that a cured film that hardly peels off or changes its appearance even under severe conditions such as boiling can be obtained. Moreover, since the cured film obtained is excellent also in hardness and scratch resistance, the active energy ray-curable resin composition of the present invention is suitable for a coating agent, particularly a coating material for a metal substrate.

The present invention is described in detail below.
In the present invention, (meth) acryl means acryl or methacryl, (meth) acryloyl means acryloyl or methacryloyl, and (meth) acrylate means acrylate or methacrylate.

[Urethane (meth) acrylate compound (A)]
The urethane (meth) acrylate compound (A) in the present invention is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a1), a polyvalent isocyanate compound (a2), and a polyol compound (a3). And having a structural site derived from the polyol compound (a3) in the structure. The urethane (meth) acrylate compound (A) may be used alone or in combination of two or more.

Examples of the hydroxyl group-containing (meth) acrylate compound (a1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) ) Acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri (meth) acrylate, caprolactone-modified penta Erythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, etc. Is mentioned.
Among these, a hydroxyl group (meth) acrylate-based compound having one ethylenically unsaturated group is preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable in terms of excellent reactivity and versatility.
Moreover, these can be used 1 type or in combination of 2 or more types.

Examples of the polyvalent isocyanate compound (a2) include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Aliphatic polyisocyanates such as polyisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (Isocyanatomethyl) Cycloaliphatic polyisocyanates such as hexane, trimer compounds or multimeric compounds of these polyisocyanates, allophanate type polyisocyanates, burette type polyisocyanates, water-dispersed polyisocyanates (for example, manufactured by Nippon Polyurethane Industry Co., Ltd.) "Aquanate 100", "Aquanate 110", "Aquanate 200", "Aquanate 210", etc.).
Among these, cycloaliphatic polyisocyanate compounds are preferably used, and in particular, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate have less yellowing of the cured coating film and less curing shrinkage. It is further preferably used in terms of points.

  Examples of the polyol compound (a3) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, (meth) acrylic polyols, polysiloxane polyols, and the like.

  Examples of polyether polyols include polyether polyols containing alkylene structures such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Is mentioned.

Examples of the polyester-based polyol include a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. And reactants.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl. Methylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol).
Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, trimellitic acid, and the like.
Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

Examples of the polycarbonate-based polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymerization product of a cyclic carbonate (such as alkylene carbonate).
Examples of the polyhydric alcohol include polyhydric alcohols exemplified in the description of the polyester-based polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. It is done.
In addition, the polycarbonate polyol should just be a compound which has a carbonate bond in a molecule | numerator, and the terminal is a hydroxyl group, and may have an ester bond with a carbonate bond.

  Examples of the polyolefin-based polyol include those having a saturated hydrocarbon skeleton having a homopolymer or copolymer such as ethylene, propylene and butene, and having a hydroxyl group at the molecular end.

Examples of the polybutadiene-based polyol include those having a butadiene copolymer as a hydrocarbon skeleton and having a hydroxyl group at the molecular end.
The polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in the structure thereof are hydrogenated.

  Examples of the (meth) acrylic polyol include those having at least two hydroxyl groups in the molecule of the polymer or copolymer of the (meth) acrylic acid ester. , For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid Examples include 2-ethylhexyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid alkyl esters such as octadecyl (meth) acrylic acid, and the like.

  Examples of the polysiloxane polyol include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.

  Among these, polyester-based polyols and polyether-based polyols are preferable, and polyester-based polyols are particularly preferable in terms of excellent mechanical properties such as flexibility during curing.

  As a molecular weight of the polyol type compound (a3) used by this invention, 500-8000 are preferable, Especially preferably, it is 550-5000, More preferably, it is 600-3000. If the molecular weight of the polyol (a3) is too large, mechanical properties such as coating film hardness tend to be reduced during curing, and if it is too small, curing shrinkage tends to be large and stability tends to be lowered.

  The production method of the urethane (meth) acrylate compound (A) is usually the above hydroxyl group-containing (meth) acrylate compound (a1), polyvalent isocyanate compound (a2), polyol compound (a3) in a reactor. The reaction product obtained by reacting the polyol compound (a3) and the polyvalent isocyanate compound (a2) in advance may be added to the hydroxyl group-containing (meth) acrylate compound (a1). ) Is useful in terms of reaction stability and reduction of by-products.

  For the reaction between the polyol compound (a3) and the polyvalent isocyanate compound (a2), known reaction means can be used. At that time, for example, the molar ratio of the isocyanate group in the polyvalent isocyanate compound (a2) to the hydroxyl group in the polyol (a3) is usually about 2n: (2n-2) (n is an integer of 2 or more). Thus, after obtaining a terminal isocyanate group-containing urethane (meth) acrylate compound having an isocyanate group remaining, an addition reaction with the hydroxyl group-containing (meth) acrylate compound (a1) is made possible.

  The addition reaction of the reaction product obtained by reacting the polyol compound (a3) and the polyvalent isocyanate compound (a2) in advance with the hydroxyl group-containing (meth) acrylate compound (a1) is also a known reaction. Means can be used.

The reaction molar ratio between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a1) is, for example, that the polyisocyanate compound (a2) has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (a1). ) Has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (a1) is about 1: 2, and the polyisocyanate compound (a2) has three isocyanate groups. When the hydroxyl group-containing (meth) acrylate compound (a1) has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (a1) is about 1: 3.
In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a1), the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. A (meth) acrylate compound (A) is obtained.

  In the reaction between the polyol (a3) and the polyvalent isocyanate compound (a2), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a1), a catalyst is used for the purpose of promoting the reaction. Examples of such catalysts include organic metal compounds such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, zinc octenoate, tin octenoate, cobalt naphthenate, stannous chloride, and chloride. Metal salts such as stannic, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, N ′ -Amine-based catalysts such as tetramethyl-1,3-butanediamine, N-ethylmorpholine, bismuth nitrate, bismuth bromide, Organic bismuth compounds such as dibutyl bismuth dilaurate, dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, etc. Organic acid bismuth salts such as salts, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, bismuth digallate, etc. Among them, dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are preferable.

  In the reaction of the polyol (a3) with the polyvalent isocyanate compound (a2), and further in the reaction of the reaction product with the hydroxyl group-containing (meth) acrylate compound (a1), a functional group that reacts with an isocyanate group. For example, organic solvents such as esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic solvents such as toluene and xylene can be used.

  Moreover, reaction temperature is 30-90 degreeC normally, Preferably it is 40-80 degreeC, and reaction time is 2 to 10 hours normally, Preferably it is 3 to 8 hours.

The urethane (meth) acrylate compound (A) used in the present invention preferably has two or more ethylenically unsaturated groups, and preferably has three or more ethylenically unsaturated groups. Is more preferable, and further having 4 or more ethylenically unsaturated groups is further preferable from the viewpoint of the hardness of the cured coating film.
Moreover, the upper limit of the ethylenically unsaturated group which a urethane (meth) acrylate type compound (A) contains is 30 normally, Preferably it is 25 or less.

  The weight average molecular weight of the obtained urethane (meth) acrylate compound (A) is preferably 500 to 50000, and more preferably 1000 to 30000. If the weight average molecular weight is too small, the cured coating film tends to be brittle, and if it is too large, the viscosity tends to be high and difficult to handle.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, and high performance liquid chromatography (The Japan Waters company make "Waters 2695 (main body)" and "Waters 2414 (detector)"), Column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / pack, packing material: styrene-divinylbenzene copolymer, packing It is measured by using three series of agent particle size: 10 μm).

The viscosity of the urethane (meth) acrylate compound (A) at 60 ° C. is preferably 500 to 150,000 mPa · s, particularly 500 to 120,000 mPa · s, more preferably 1,000 to 100,000 mPa · s. It is preferable. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured with an E-type viscometer.

[Urethane (meth) acrylate compound (B)]
The urethane (meth) acrylate compound (B) in the present invention is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (b1) and a polyvalent isocyanate compound (b2), and only one kind is used alone. It may be used in combination, or two or more may be used in combination.

Examples of the hydroxyl group-containing (meth) acrylate compound (b1) include those similar to the hydroxyl group-containing (meth) acrylate compound (a1), such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl. Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- ( (Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyester Lenglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxy Propyl methacrylate, pentaerythritol tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) Examples thereof include acrylate and ethylene oxide-modified dipentaerythritol penta (meth) acrylate.
Among these, it is preferable to use one or more compounds containing 3 or more ethylenically unsaturated groups from the viewpoint of the hardness of the cured coating film. Furthermore, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meta) It is particularly preferred to use acrylates).

Examples of the polyvalent isocyanate compound (b2) include those similar to the above polyisocyanate compound (a2), such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diene. Aromatic polyisocyanates such as isocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, Hydrogenated xylylene diisocyanate, isophorone diisocyanate, nor Runene diisocyanate, alicyclic polyisocyanate such as 1,3-bis (isocyanatomethyl) cyclohexane, or trimer compound or multimer compound of these polyisocyanates, allophanate type polyisocyanate, burette type polyisocyanate, water dispersion Type polyisocyanate (for example, “Aquanate 100”, “Aquanate 110”, “Aquanate 200”, “Aquanate 210”, etc., manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like.
Among these, cycloaliphatic polyisocyanate compounds are preferably used, and in particular, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate have less yellowing of the cured coating film and less cure shrinkage. And more preferably.

The urethane (meth) acrylate compound (B) used in the present invention preferably has 3 or more ethylenically unsaturated groups from the viewpoint of the hardness of the cured coating film, and preferably 4 or more ethylenically unsaturated groups. Particularly preferred are those having a saturated group, more preferred are those having 6 or more ethylenically unsaturated groups, and among them, 6 obtained by reacting pentaerythritol tri (meth) acrylate with isophorone diisocyanate. The urethane (meth) acrylate having an ethylenically unsaturated group is particularly preferred.
Moreover, the upper limit of the ethylenically unsaturated group which a urethane (meth) acrylate type compound (B) contains is 30 normally, Preferably it is 25 or less.

  In order to adjust the number of ethylenically unsaturated groups, the hydroxyl group-containing (meth) acrylate compound (b1) and the polyvalent isocyanate compound (b2) may be appropriately selected and used. When using a hydroxyl group-containing (meth) acrylate compound (b1) having three ethylenically unsaturated groups and using a diisocyanate compound as the polyvalent isocyanate compound (b2), urethane (meth) acrylate The number of ethylenically unsaturated groups in the system compound (B) is six.

A urethane (meth) acrylate type compound (B) can be prepared by manufacturing according to the manufacturing method of the said urethane (meth) acrylate type compound (A).
do it.

The reaction molar ratio between the polyvalent isocyanate compound (b2) and the hydroxyl group-containing (meth) acrylate compound (b1) is, for example, that the polyisocyanate compound (b2) has two isocyanate groups and has a hydroxyl group content ( When the hydroxyl group of the (meth) acrylate compound (b1) is one, the polyvalent isocyanate compound (b2): hydroxyl group-containing (meth) acrylate compound (b1) is about 1: 2, and the polyisocyanate compound When the compound (b2) has three isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (b1) has one hydroxyl group, the polyvalent isocyanate compound (b2): hydroxyl group-containing (meth) acrylate compound (B1) is about 1: 3.
In the addition reaction between the polyvalent isocyanate compound (b2) and the hydroxyl group-containing (meth) acrylate compound (b1), the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. By making it, a urethane (meth) acrylate type compound (B) is obtained.

  The weight average molecular weight of the obtained urethane (meth) acrylate compound (B) is preferably 500 to 50000, more preferably 1000 to 30000. If the weight average molecular weight is too small, the cured coating film tends to be brittle, and if it is too large, the viscosity tends to be high and difficult to handle.

  The weight average molecular weight is measured in the same manner as described above.

The viscosity of the urethane (meth) acrylate compound (B) at 60 ° C. is preferably 500 to 150,000 mPa · s, particularly 500 to 120,000 mPa · s, more preferably 1,000 to 100,000 mPa · s. It is preferable. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured with an E-type viscometer.

As the total amount (sum of (A) and (B)) of the urethane (meth) acrylate compound (A) and the urethane (meth) acrylate compound (B) in the active energy ray-curable resin composition, (A ) To (E) When the total of the components is 100 parts by weight, it is preferably 10 to 80 parts by weight, particularly preferably 20 to 75 parts by weight, and particularly preferably 30 to 70 parts by weight.
If the total amount of the urethane (meth) acrylate compound (A) and the urethane (meth) acrylate compound (B) is too small, the pencil hardness and scratch resistance tend to decrease. Tend to decrease.

Moreover, as a content ratio (weight ratio) of the urethane (meth) acrylate compound (A) and the urethane (meth) acrylate compound (B), (A) :( B) = 1: 0.1 to 1: 2 And (A) :( B) = 1: 0.3 to 1: 1.9, particularly preferably (A) :( B) = 1: 0.5 to 1: 1. .8, and more preferably (A) :( B) = 1: 0.7 to 1: 1.7.
If the content ratio of the urethane (meth) acrylate compound (B) is too large, the adhesiveness tends to decrease or the curing shrinkage tends to increase, and if it is too small, the viscosity increases, and the machine has scratch resistance, hardness, etc. The physical properties tend to be reduced.

[Acrylic resin (C)]
The acrylic resin (C) in the present invention is obtained by polymerizing a monomer component containing a (meth) acrylic monomer. As for acrylic resin (C), only 1 type may be used independently and 2 or more types may be used together.
The acrylic resin (C) preferably contains, as a polymerization component, a (meth) acrylic acid ester monomer (c1) as a main component, and if necessary, a functional group-containing monomer (c2) and other copolymers. The polymerizable monomer (c3) can also be used as a copolymerization component.

  Examples of the (meth) acrylic acid ester monomer (c1) include aliphatic (meth) acrylic acid ester monomers such as (meth) acrylic acid alkyl esters and aromatic (meth) acrylic acid phenyl esters ( And (meth) acrylic acid ester monomers.

  About this (meth) acrylic acid alkyl ester, it is preferable that carbon number of an alkyl group is 1-12 normally, especially 1-8, Furthermore, it is preferable that it is 4-8, Specifically, methyl (meth) acrylate , Ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. Can be mentioned. Examples of (meth) acrylic acid phenyl ester include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.

  Other (meth) acrylic acid ester monomers include tetrahydrofurfuryl (meth) acrylate and the like. These can be used alone or in combination of two or more.

  Among these (meth) acrylic acid ester monomers (c1), methyl (meth) acrylate, n-butyl (meth) acrylate, 2 in terms of copolymerizability, adhesive physical properties, ease of handling, and availability of raw materials. -Ethylhexyl (meth) acrylate is preferably used.

  Examples of the functional group-containing monomer (c2) include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an alkoxy group or phenoxy group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, a nitrogen-containing monomer, a glycidyl group-containing monomer, and phosphoric acid. Examples thereof include a group-containing monomer and a sulfonic acid group-containing monomer, which are used alone or in combination.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters, caprolactone-modified 2-hydroxyethyl (meth) acrylate, etc. Monomers containing primary hydroxyl groups such as caprolactone-modified monomers, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc. 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3 -Secondary hydroxyl group-containing monomers such as phenoxypropyl (meth) acrylate; tertiary hydroxyl group-containing monomers such as 2,2-dimethyl-2-hydroxyethyl (meth) acrylate.

  Further, polyethylene glycol derivatives such as diethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate, poly (ethylene Oxyalkylene-modified monomers such as glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate may be used.

  Examples of the carboxyl group-containing monomer include Michael addition of acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, and (meth) acrylic acid. (Eg, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.), 2- (meth) acryloyloxyethyl dicarboxylic acid monoester (eg, 2-acryloyloxyethyl) Succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahi Rofutaru acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid mono ester) and the like. Such a carboxyl group-containing monomer may be used as an acid, or may be used in the form of a salt neutralized with an alkali.

  Examples of the alkoxy group-containing monomer include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and 2-butoxydiethylene glycol. (Meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol- Polypropylene glycol-mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearo Aliphatic (meth) acrylic acid esters such as xypolyethylene glycol mono (meth) acrylate and the like. Examples of the phenoxy group-containing monomer include 2-phenoxyethyl (meth) acrylate and phenoxypolyethylene glycol (meth) acrylate. And acrylic acid esters of aromatic (meth) acrylates such as phenoxypolyethylene glycol-polypropylene glycol- (meth) acrylate and nonylphenol ethylene oxide adduct (meth) acrylate.

  Examples of the amide group-containing monomer include acrylamide, methacrylamide, N- (n-butoxyalkyl) acrylamide, N- (n-butoxyalkyl) methacrylamide, N, N-dimethyl (meth) acrylamide, N, N- Examples include diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, acrylamide-3-methylbutylmethylamine, dimethylaminoalkylacrylamide, and dimethylaminoalkylmethacrylamide.

  Examples of the amino group-containing monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and a quaternized product thereof.

  Examples of the nitrogen-containing monomer include acryloylmorpholine.

  Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.

  Examples of the phosphoric acid group-containing monomer include 2- (meth) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxyethyl) acid phosphate, and the like.

Examples of the sulfonic acid group-containing monomer include olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, and salts thereof. .
These functional group-containing monomers (c2) may be used alone or in combination of two or more.

  Examples of the other copolymerizable monomer (c3) include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, Examples include vinyl pyridine, vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, and dimethylallyl vinylketone.

  For the purpose of increasing the molecular weight, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate A compound having two or more ethylenically unsaturated groups such as divinylbenzene can also be used in combination.

  In the acrylic resin (C), the content ratio of the (meth) acrylic acid ester monomer (c1), the functional group-containing monomer (c2), and the other copolymerizable monomer (c3) is (meth) acrylic acid ester monomer (C1) is preferably 10 to 100% by weight, particularly preferably 20 to 95% by weight, and the functional group-containing monomer (c2) is preferably 0 to 90% by weight, particularly preferably 5 to 80% by weight, and other copolymerizable properties. The monomer (c3) is preferably 0 to 50% by weight, particularly preferably 5 to 40% by weight.

  The acrylic resin (C) in the present invention is preferably a polymer having methyl (meth) acrylate as a polymerization component in view of excellent compatibility with urethane (meth) acrylate, and particularly methyl methacrylate as a polymerization component. It is preferable that the polymer is polymethyl methacrylate.

  In the present invention, the acrylic resin (C) is produced by polymerizing the monomer components (c1) to (c3). In the polymerization, solution radical polymerization, suspension polymerization, bulk polymerization, It can be performed by a conventionally known method such as emulsion polymerization. For example, in an organic solvent, a polymerization monomer such as the (meth) acrylic acid ester monomer (c1), a functional group-containing monomer (c2), other copolymerizable monomer (c3), a polymerization initiator (azobisisobutyrate) Ronitrile, azobisisovaleronitrile, benzoyl peroxide, etc.) are mixed or dropped and polymerized at reflux or at 50 to 90 ° C. for 2 to 20 hours.

  The glass transition temperature (Tg) of acrylic resin (C) is 40-120 degreeC normally, Preferably it is 60-110 degreeC. When the glass transition temperature is too high, the thermal shrinkage mitigating action of the cured coating film tends to decrease, and when it is too low, the thermal durability of the cured coating film tends to decrease.

  The weight average molecular weight of the acrylic resin (C) thus obtained is usually 10,000 to 3,000,000, preferably 30,000 to 2.5 million.

  Further, the degree of dispersion (weight average molecular weight / number average molecular weight) of the acrylic resin (C) is preferably 20 or less, particularly preferably 15 or less, and further preferably 10 or less.

In addition, said weight average molecular weight and number average molecular weight are based on standard polystyrene molecular weight conversion, and it is based on high performance liquid chromatography (Nippon Waters, "Waters 2695 (main body)" and "Waters 2414 (detector)"). Column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / pack, filler material: styrene-divinylbenzene copolymer, It is measured by using three series of filler particle diameters: 10 μm), and the degree of dispersion is determined from the weight average molecular weight and the number average molecular weight. The glass transition temperature is calculated from the Fox equation.

The content of the acrylic resin (C) is preferably 10 to 200 parts by weight, particularly preferably 20 to 150 parts when the total of the components (A) and (B) is 100 parts by weight. Part by weight, particularly preferably 50 to 120 parts by weight.
When there is too little content of acrylic resin (C), there exists a tendency for adhesiveness to fall or hardening shrinkage | contraction to become large, and when too large, there exists a tendency for mechanical physical properties, such as scratch resistance, to fall.

[Polysaccharide derivative (D)]
The polysaccharide derivative (D) in the present invention includes homopolysaccharides and heteropolysaccharides. For example, α-1,4
-Glucan (amylose, amylopectin), α-1,6-glucan (dextran), β-1,4-glucan (cellulose), β-1,6-glucan (pustulan), β-1,3-glucan (eg , Curdlan, dizophyllan, etc.), α-1,3-glucan, β-1,2-glucan (Crown Gall polysaccharide) and other α- or β-glucan derivatives, β-1,4-galactan, β-1, 4-mannan, α-1,6-mannan, β-1,2-fructan (inulin), β-2,6-fructan (levan), β-1,4-xylan, β-1,3-xylan, Examples include β-1,4-chitosan, β-1,4-N-acetylchitosan (chitin), pullulan, agarose, alginic acid, and the like, and starch containing amylose is also included. Preferred are α- or β-glucan derivatives in terms of excellent compatibility with the acrylic resin (C), and more preferred are β-glucan derivatives, particularly cellulose derivatives.

  As the polysaccharide derivative (D), all or part of the hydroxyl groups of the polysaccharide may be —OC (O) R, —OC (O) NH (R), —OC (O) N (R) (R) and —OR. Those substituted with other substituents such as are preferred. Here, R is an aliphatic group having 1 to 3 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, or an aromatic or heteroaromatic group having 4 to 20 carbon atoms, and R itself is a substituent. It may be optionally substituted. One or more kinds of other substituents may be substituted. More preferred polysaccharide derivatives include acylated polysaccharides. Preferred acyl groups of the acylated polysaccharide include acetyl, butyryl, benzoyl, methylbenzoyl, dimethylbenzoyl, chlorobenzoyl, dichlorobenzoyl groups. As a suitable polysaccharide derivative (D), a cellulose-acetate-butyrate resin etc. can be mentioned, for example. These polysaccharide derivatives (D) may be used alone or in combination of two or more.

The content of the polysaccharide derivative (D) is usually 0.1 to 60 parts by weight, preferably 1 to 50 parts by weight, particularly 100 parts by weight of the total of the components (A) and (B). Preferably it is 10-40 weight part.
If the content of the polysaccharide derivative (D) is too large, the leveling property of the coating tends to be extremely lowered, and the UV crosslinking component ratio is lowered, so that sufficient surface hardness tends not to be obtained. On the other hand, if the content of the polysaccharide derivative (D) is too small, there is a tendency that heat shrinkage cannot be alleviated at the time of curing shrinkage during UV curing and durability evaluation of the coating film.

[Phosphoric group-containing ethylenically unsaturated compound (E)]
Examples of the phosphoric acid group-containing ethylenically unsaturated compound (E) in the present invention include 2- (meth) acryloyloxyethyl phosphate, ethylene phosphate (meth) acrylate, trimethylene phosphate (meth) acrylate, and phosphoric acid 1 -Phosphoric acid group-containing ethylenically unsaturated compound having one ethylenically unsaturated group such as chloromethylethylene (meth) acrylate, bis (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide-modified phosphoric acid diacrylate And phosphoric acid group-containing ethylenically unsaturated compounds having two or more ethylenically unsaturated groups such as ethylene oxide-modified phosphoric acid di (meth) acrylate and ethylene oxide-modified phosphoric acid tri (meth) acrylate. Only one phosphoric acid group-containing ethylenically unsaturated compound (E) may be used alone, or two or more may be used in combination.
Among them, it is preferable to use a compound having two or more ethylenically unsaturated groups from the viewpoint of scratch resistance, and bis (2- (meth) acryloyloxyethyl) phosphate is particularly preferable, and bis (2-methacrylic acid) is particularly preferable. Loyloxyethyl) phosphate is preferred in terms of substrate adhesion.

The content of the phosphoric acid group-containing ethylenically unsaturated compound (E) is 0.1 to 20 parts by weight when the total of the component (A) and the component (B) is 100 parts by weight. The amount is particularly preferably 0.2 to 15 parts by weight, particularly preferably 0.3 to 10 parts by weight.
If the content of the phosphoric acid group-containing ethylenically unsaturated compound (E) is too small, the adhesion tends to decrease. If the content is too large, the substrate is corroded, and mechanical properties such as scratch resistance and hardness are reduced. There is a tendency to decrease.

[Photopolymerization initiator (F)]
In the present invention, a urethane (meth) acrylate compound (A), a urethane (meth) acrylate compound (B), an acrylic resin (C), a polysaccharide derivative (D), and a phosphate group-containing ethylenically unsaturated compound In addition to (E), it is also preferable to contain a photopolymerization initiator (F) in terms of exhibiting the effects of the present invention.

  Examples of the photopolymerization initiator (F) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2- Hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino) Acetophenones such as phenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether Benzoin etc. Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2, 4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride, etc. Benzophenones: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy)- 3,4- Thioxanthones such as methyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphos Acylphosphine oxides such as fin oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; In addition, as for these photoinitiators (F), only 1 type may be used independently and 2 or more types may be used together.

  These auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.

  Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.

The content of the photopolymerization initiator (F) is preferably 0.1 to 40 parts by weight, particularly preferably when the total of the component (A) and the component (B) is 100 parts by weight. 1 to 20 parts by weight, particularly preferably 2 to 20 parts by weight.
If the content of the photopolymerization initiator (F) is too small, curing tends to be poor, and if it is too much, mechanical properties such as scratch resistance and hardness tend to be reduced, and embrittlement and coloring problems occur. Tend to occur.

  In the present invention, in addition to the components (A) to (E) and (F), an ethylenically unsaturated monomer, a surface conditioner, a leveling agent, a polymerization inhibitor, etc. may be added as necessary. it can.

  As the ethylenically unsaturated monomer, for example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer, and the like can be used.

  As said monofunctional monomer, what is necessary is just a monomer containing one ethylenically unsaturated group, for example, styrene, vinyl toluene, chlorostyrene, (alpha) -methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, Acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate Lilate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate , Octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified ( Of phthalic acid derivatives such as (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate Half ester (meth) acrylate, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N -Methylol (meth) acrylamide, N-vinyl pyrrolidone, 2-vinyl pyridine, 2- (meth) acryloyloxyethyl acid phosphate monoester, etc. are mentioned.

  The bifunctional monomer may be any monomer containing two ethylenically unsaturated groups. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene Oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,6-hexanediol ethylene oxide modified di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di ( Meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate, 2- (meth) acryloyloxyethyl acid phosphate diester, etc. It is done.

  The tri- or higher functional monomer may be any monomer containing three or more ethylenically unsaturated groups. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, Glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ethylene oxide modified dipentaerythritol (Meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, succinic acid modified pentaerythritol tri (meth) acrylate Etc.

  Examples of the ethylenically unsaturated monomer include, in addition to the above, a Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester, and examples of the Michael adduct of acrylic acid include acrylic acid dimer, methacrylic acid dimer, Examples include acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, and methacrylic acid tetramer. Examples of the 2-acryloyloxyethyl dicarboxylic acid monoester that is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyloxy. Examples thereof include ethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester, and the like. Furthermore, oligoester acrylate is also mentioned.

  The content of the ethylenically unsaturated monomer is preferably 1 to 100 parts by weight, particularly preferably 10 to 80 parts by weight, when the total of the component (A) and the component (B) is 100 parts by weight. Parts, particularly preferably 20 to 60 parts by weight.

  The surface conditioner is not particularly limited, and examples thereof include alkyd resins. Such an alkyd resin has an effect of imparting a film-forming property at the time of application and an effect of increasing the adhesion to a metal vapor deposition surface.

  As the leveling agent, a known general leveling agent can be used as long as it has a wettability imparting action to the base material of the coating liquid and a surface tension reducing action. For example, a silicone-modified resin, a fluorine-modified resin, An alkyl-modified resin or the like can be used.

  Examples of the polymerization inhibitor include p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t- Examples thereof include butyl hydroquinone and pt-butyl catechol.

  The active energy ray-curable resin composition of the present invention includes oil, antioxidant, flame retardant, antistatic agent, filler, stabilizer, reinforcing agent, matting agent, abrasive, inorganic particles (silica Etc.) can also be blended.

  Thus, the urethane (meth) acrylate compound (A), urethane (meth) acrylate compound (B), acrylic resin (C), polysaccharide derivative (D), and phosphate group-containing ethylenically unsaturated compound (E) of the present invention. ) -Containing active energy ray-curable resin composition.

  Such a resin composition can be used by blending an organic solvent and adjusting the viscosity as necessary. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene, xylene Aromatic glycols such as propylene glycol monomethyl ether, acetates such as ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more.

  When two or more types are used in combination, a combination of glycol ethers such as propylene glycol monomethyl ether and ketones such as methyl ethyl ketone and alcohols such as methanol, a combination of ketones such as methyl ethyl ketone and alcohols such as methanol, methanol From the viewpoint of the appearance of the coating film, it is preferable to use two or more alcohols such as alcohols in combination.

  The resin composition of the present invention can be usually diluted to 10 to 60% by weight, preferably 20 to 40% by weight, using the organic solvent, and applied to a substrate.

In producing the active energy ray-curable resin composition of the present invention, urethane (meth) acrylate compound (A), urethane (meth) acrylate compound (B), acrylic resin (C), polysaccharide derivative ( The mixing method of D), the phosphoric acid group-containing ethylenically unsaturated compound (E), and the photopolymerization initiator (F) is not particularly limited, and can be mixed by various methods.
Among them, a method in which (A) and (B) are mixed, (C) and (D) are added, (E) is added, and (F) is finally added. Further, ethyl acetate, After making a solution in which (A) and (B) were dissolved in an organic solvent such as toluene, (C) and (D) dissolved in the organic solvent were added thereto, and (E) was added thereto, The method of adding (F) is particularly preferable.

  The active energy ray curable resin composition of the present invention is effectively used as a curable resin composition for coating film formation, such as a topcoat agent and an anchor coat agent on various substrates, and is active energy ray curable. After the mold resin composition is applied to the base material (when the composition diluted with an organic solvent is applied, it is further dried) and then cured by irradiation with active energy rays. The coating method is not particularly limited, and examples thereof include wet coating methods such as spray, shower, dipping, roll, spin, screen printing, and the like.

  As such active energy rays, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous from the viewpoint of easy availability and price. In addition, when performing electron beam irradiation, it can harden | cure even without using a photoinitiator (F).

As a method of curing by ultraviolet irradiation, using a high pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc. What is necessary is just to irradiate about 30-3000mJ / cm < ² >.
After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

  The coating film thickness (film thickness after curing) is usually preferably 1 to 50 μm, particularly preferably 3 to 30 μm. In particular, in the case of thin coating, it is preferably 1 to 15 μm, and in the case of thick coating, it is preferably 15 to 30 μm, particularly preferably 15 to 25 μm. If the coating film thickness is too thick, the heat shrinkage of the cured coating film tends to increase in a durability test in which a heat load such as a boiling water immersion test is large, and the adhesion to the substrate tends to be reduced. On the other hand, if it is too thin, there is a tendency that the target surface hardness as a UV cured film cannot be obtained.

Examples of the substrate on which the active energy ray-curable resin composition of the present invention is applied include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile butadiene styrene copolymers (ABS), polystyrene resins, and the like. These molded products (films, sheets, cups, etc.), metals, glass and the like can be mentioned.
The active energy ray-curable resin composition of the present invention has excellent adhesion performance to these substrates, but it is particularly difficult to obtain sufficient adhesion with ordinary coating agents. Even when the material is a metal, it has excellent metal adhesion.

Examples of such a metal include aluminum, copper, iron, SUS, zinc, magnesium, and alloys thereof. Particularly, the metal exhibits remarkable effects on aluminum, magnesium, alloys thereof, and SUS.
The metal substrate may be subjected to surface treatment such as annealing, quenching, normalizing, and tempering such as bright annealing (BA); plating finishing, etching, and dry coating. . For example, the effect of the present invention becomes more remarkable by applying the active energy ray-curable resin composition of the present invention to a stainless steel substrate subjected to bright annealing treatment such as SUS430BA or SUS304BA. .

  Urethane (meth) acrylate compound (A), urethane (meth) acrylate compound (B), acrylic resin (C), polysaccharide derivative (D), phosphate group-containing ethylenically unsaturated compound (D) of the present invention The active energy ray-curable resin composition containing bismuth is excellent in adhesion to metal substrates such as aluminum and SUS, and even when coated on a metal substrate with a relatively thick film thickness. In addition, there is an excellent effect that a cured film is obtained that does not easily peel off or change its appearance even under severe conditions such as when the coated metal substrate is boiled. The active energy ray-curable resin composition of the present invention includes paints, pressure-sensitive adhesives, adhesives, adhesives, inks, protective coating agents, anchor coating agents, magnetic powder coating binders, sandblast coatings, plate materials, etc. It is useful as various film forming materials. Among them, it is very useful to use it as a metal-based coating agent.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the examples, “parts” and “%” mean weight basis unless otherwise specified.

-The following were prepared as urethane (meth) acrylate (A-1).
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 37.2 g (0.17 mol) of isophorone diisocyanate, 12.9 g of a trifunctional polyester polyol (hydroxyl value 260 mgKOH / g) .02 mol), bifunctional polyether polyol (hydroxyl value 175 mg KOH / g) 25.6 g (0.04 mol), 2-hydroxyethyl acrylate 25.8 g (0.22 mol), hydroquinone methyl ether 0 as a polymerization inhibitor 0.02 g of dibutyltin dilaurate as a reaction catalyst was charged and reacted at 60 ° C. for 3 hours. When the residual isocyanate group reached 0.3%, the reaction was terminated, and a 2-3 functional urethane acrylate (A-1 )

-The following were prepared as urethane (meth) acrylate (B-1).
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 19.3 g (0.09 mol) of isophorone diisocyanate, 96.3 g of pentaerythritol triacrylate (hydroxyl value 105 mg KOH / g) 18 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were allowed to react at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group reached 0.3%. , 6 functional urethane acrylate (B-1) was obtained.

-The following were prepared as acrylic resin (C-1).
To a reactor equipped with a stirrer, a reflux device, a dropping funnel and a nitrogen introduction tube, 50.0 g of toluene (solvent) was added, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. Next, 50.0 g of methyl methacrylate and a mixture added with an appropriate amount of azobisisobutyronitrile as a polymerization initiator were added dropwise over 2.0 hours, and further maintained at the same temperature for 1.0 hour to complete the polymerization, A solution (concentration 50%) of acrylic resin (C-1) was obtained. The weight average molecular weight (polystyrene conversion) of the obtained (C-1) was 45,000, and the glass transition temperature (Tg) was 100 ° C.

  -As the polysaccharide derivative (D-1), a cellulose-acetate-butyrate resin (manufactured by Eastman Chemical Japan Co., Ltd .: trade name “CAB381-20”) was used.

  -As the phosphoric acid group-containing ethylenically unsaturated compound (E-1), bis (2- (meth) acryloyloxyethyl) phosphate (manufactured by Kyoeisha Chemical Co., Ltd., “Light Ester P-2M”) was used.

  As the photopolymerization initiator (F-1), 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Japan, “Irgacure 184”) was used.

[Examples 1-2, Comparative Examples 1-3]
Urethane (meth) acrylate compound (A-1), urethane (meth) acrylate compound (B-1), acrylic resin (C-1), polysaccharide derivative (D-1), phosphate group-containing ethylene An unsaturated compound (E-1) and a photopolymerization initiator (F-1) are blended at a ratio shown in Table 1 in terms of solid content, and the solid content excluding the photopolymerization initiator with butyl acetate is 40%. The active energy ray-curable resin composition was obtained. The following evaluation was performed about the obtained active energy ray hardening-type resin composition.

<Base material adhesion>
The active energy ray-curable resin composition obtained above is applied to SUS304BA (JIS G4305) manufactured by Nippon Test Panel Co., Ltd. so that the film thickness after drying becomes the film thickness shown in Table 2. After drying at 60 ° C. for 5 minutes, using a high pressure mercury lamp lamp 80W and one lamp, UV irradiation of 2 passes at a conveyor speed of 5.1 m / min from a height of 18 cm (accumulated dose 500 mJ / cm ² ) to form a cured coating film. About the cured coating film, base-material adhesiveness was evaluated by the cross-cut tape method according to JISK5400 (1990 edition). The results are shown in Table 2.

<Boiling water resistance>
The active energy ray-curable resin composition obtained above is applied to SUS304BA (JIS G4305) manufactured by Nippon Test Panel Co., Ltd. so that the film thickness after drying becomes the film thickness shown in Table 2. After drying at 60 ° C. for 5 minutes, using a high pressure mercury lamp lamp 80W and one lamp, UV irradiation of 2 passes at a conveyor speed of 5.1 m / min from a height of 18 cm (accumulated dose 500 mJ / cm ² ) to form a cured coating film. The cured coating film formed on the SUS304BA (JIS G4305) was immersed in boiling water for 1 hour, and the surface state of the coating film was observed. Further, the adhesion to the substrate was evaluated by the cross-cut tape method according to JIS K 5400 (1990 edition) in the same manner as described above. The appearance of the coating film was evaluated according to the following evaluation criteria. The results are shown in Table 2.
<Appearance of coating film>
○: There was no change.
Δ: The coating film partially whitened.
X: The coating film was whitened.

  As shown in Table 1, in the active energy ray-curable resin compositions of Examples 1 and 2, the adhesion to the substrate and the coating film after the boiling water resistance test both in the thick film (20 μm) and the thin film (10 μm) A film having an excellent appearance can be obtained. On the other hand, the comparative example 1 which does not contain a polysaccharide derivative (D), the comparative example 2 which does not contain the urethane (meth) acrylate type compound (B) which does not have a structural part derived from a polyol component, and the urethane which has a structural part derived from a polyol component ( In Comparative Example 3 not containing the (meth) acrylate compound (A), a coating film having poor substrate adhesion and coating film appearance after the boiling water resistance test was obtained.

  The active energy ray-curable resin composition of the present invention is excellent in coating film hardness and further exhibits an effect of excellent curability, and is a paint, a pressure-sensitive adhesive, an adhesive, an adhesive, an ink, and a protective coating. It is useful as various film forming materials such as a coating agent, an anchor coating agent, a magnetic powder coating binder, a sandblast coating, and a plate material. Among them, it is very useful to use as a coating agent for metal substrates.

Claims (8)

A urethane (meth) acrylate compound (A) obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a1), a polyvalent isocyanate compound (a2), and a polyol compound (a3);
A urethane (meth) acrylate compound (B) obtained by reacting a hydroxyl group-containing (meth) acrylate compound (b1) and a polyvalent isocyanate compound (b2);
Acrylic resin (C),
Polysaccharide derivative (D) and phosphate group-containing ethylenically unsaturated compound (E)
An active energy ray-curable resin composition comprising:   2. The active energy ray-curable resin composition according to claim 1, wherein the urethane (meth) acrylate compound (B) is a urethane (meth) acrylate compound containing 6 or more ethylenically unsaturated groups. object.   The active energy ray-curable resin composition according to claim 1 or 2, wherein the acrylic resin (C) is a polymer containing methyl methacrylate as a polymerization component.   The active energy ray-curable resin composition according to claim 1, wherein the polysaccharide derivative (D) is a cellulose derivative.   The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the phosphoric acid group-containing ethylenically unsaturated compound (E) is a compound having two or more ethylenically unsaturated groups.   Furthermore, a photoinitiator (F) is contained, The active energy ray hardening-type resin composition in any one of Claims 1-5 characterized by the above-mentioned.   A coating agent comprising the active energy ray-curable resin composition according to claim 1.   The coating agent according to claim 7, which is used for a coating material for a metal substrate.