JPH083475A - Active energy ray curable resin composition - Google Patents

Abstract

PURPOSE:To produce an active energy ray-curable resin composition having a low viscosity and excellent curability and giving a coating film excellent in solvent resistance and staining resistance by combining a specified acrylic oligomer with a specified (meth)acrylate. CONSTITUTION:This composition comprises a reactive monomer having at least two (meth)acryloyl groups in the molecule and a mono(meth)acrylate represented by the formula (wherein R<1> is H or H3; and R<2> is H, CH3 or CH2CH3). It is desirable that 2-98 pts. wt. reactive oligomer is combined with 2-98 pts.wt. mono(meth)acrylate to give 100 pts.wt. mixture.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which can be cured by irradiation with active energy rays such as electron rays and ultraviolet rays.

More specifically, a coating film containing an acrylic oligomer and a mono (meth) acrylate represented by the general formula (I) as essential components and having low viscosity, excellent curability, solvent resistance and stain resistance. And a resin composition capable of forming

The resin composition of the present invention can be applied to various uses such as active energy ray-curable coating materials, printing inks and adhesives.

[0004]

2. Description of the Related Art Conventionally, thermosetting resin compositions have been used as resin compositions used in inks, paints, etc.
In recent years, from the viewpoint of energy saving, short-time curing treatment, and space saving by shortening the manufacturing process line of products, printing ink using an active energy ray-curable resin composition,
Many paints have been developed and become popular.

Specifically, active energy ray-curable resin compositions containing various acrylic esters as main components are used.

Among them, the active energy ray-curable resin composition containing low viscosity mono (meth) acrylate as a main component is
Since it is fast-curing and has good adhesion to cured products, it plays an important role as a material that imparts functionality to resins and inks.

[0007]

What has been conventionally used as a reactive diluent for an active energy ray-curable coating material is a monofunctional (meth) acrylate such as 2-ethylhexyl (meth) acrylate or 2-hydroxyethyl. Examples thereof include (meth) acrylate and ethyl carbitol (meth) acrylate, but inks and coatings containing these reactive diluents have insufficient curability, and their coating film physical properties are not always satisfactory. There wasn't.

[0008]

Means for Solving the Problems The inventors of the present invention have diligently studied to solve the above problems, and as a result, 2
A resin composition containing 2-t-butoxyalkyl (meth) acrylate obtained by introducing a t-butyl group into -hydroxyethyl (meth) acrylate as an essential component has low viscosity, excellent curability, and excellent function. It has been found that an active energy ray-curable resin composition capable of imparting properties can be obtained, and the present invention has been completed.

That is, the present invention comprises a reactive oligomer having two or more (meth) acryloyl groups in the molecule as a component A, and a mono (meth) acrylate as represented by the general formula (I) as a component B. The present invention relates to an active energy ray-curable resin composition characterized by the above.

[0010]

Embedded image

(In the formula, R ¹ represents H or CH ₃ , and R ² represents H, CH ₃ or CH ₂ CH _3. ) Hereinafter, each component of the present invention will be described in detail.

In the resin composition of the present invention, the component (A) is not particularly limited, but it is preferably selected appropriately according to the compatibility with the component (B).

The composition comprises 2 to 98 parts by weight of the component (A),
(B) component 98 to 2 parts by weight, especially (A) component 6
When used in a proportion of 0 to 80 parts by weight and 20 to 40 parts by weight of the component (B), the characteristics are exhibited well.

[Regarding Component (A)] The reactive oligomer having two or more (meth) acryloyl groups in the molecule used as the component (A) in the present invention is obtained when the component (B) is used as a diluent. The resulting composition is a component that has low viscosity, good workability, excellent curability, and imparts excellent solvent resistance and stain resistance to the cured coating film.

Specific examples of the component (A) include phthalic acid,
Polybasic acids such as adipic acid, polyhydric alcohols such as ethylene glycol and butanediol, and polyester poly (meth) acrylates obtained by reaction with (meth) acrylic acid, by reaction between epoxy resin and (meth) acrylic acid Reaction of the resulting epoxy poly (meth) acrylate, polyol, polyisocyanate, and urethane poly (meth) acrylate or polysiloxane obtained by reaction with a hydroxyl group-containing monomer such as 2-hydroxyethyl acrylate with a (meth) acrylic acid compound Examples thereof include polysiloxane poly (meth) acrylates obtained by the above, polyamide poly (meth) acrylates obtained by the reaction of polyamide with a (meth) acrylic acid compound, and the like.

Of these, urethane poly (meth) acrylate is particularly preferable because it can impart curability of the resin composition of the present invention and excellent stain resistance and solvent resistance to the cured product.

Examples of the saturated or unsaturated carboxylic acid constituting the above oligomer include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2,2- Dimethyl glutaric acid, 3,3-dimethyl glutaric acid, 3,3-diethyl glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid , 1,
4-cyclohexanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, maleic acid, fumaric acid, aconitic acid, itaconic acid, citraconic acid, mesaconic acid,
Mention may be made of muconic acid, dihydromuconic acid, and the above-mentioned halo and alkyl derivatives.

Examples of the alkyl polyol include ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol,
1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1 , 4-dimethylolcyclohexane, 2,2-diethylpropane-
1,3-diol, 3-methylpentane-1,4-diol, 2,2-diethylbutane-1,3-diol,
4,5-nonanediol diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, glycerin, pentaerythritol,
Erythritol, sorbitol, mannitol, trimethylolpropane, methylolethane, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-
Hydroxypropionate, and 2-butene-1,4
-Diols and the like.

Specific examples of the polyisocyanate include triethylene diisocyanate, ethylene diisocyanate, 1,2-diisocyanate propane, 1,3-diisocyanate propane, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate and tetramethylxylylene diisocyanate. , Hexamethylene diisocyanate, lysine isocyanate, 4,4'-
Methylene bis (cyclohexyl) isocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, dimer acid diisocyanate, 2-isocyanatoethyl-
Examples thereof include polyisocyanate monomers such as 2,6-diisocyanate hexanoate, and their dimers, trimers, and adducts with polyols.

Specific examples of the polyol used in the adduct include ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, trimethylolpropane, polytrimethylolpropane and pentaerythritol. , Polypentaerythritol, sorbitol, mannitol,
Examples thereof include alcohols such as glycerin and polyglycerin, polyether polyols, polyester polyols synthesized from polyhydric alcohols and polybasic acids, polyesters such as polycaprolactone polyols, and the like.

Specific examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 3-chloro-2-hydroxypropyl acrylate. , 3-chloro-2-hydroxypropyl methacrylate, 3-bromo-2-hydroxypropyl acrylate, 3-bromo-2-hydroxypropyl methacrylate, 2-chloro-1- (hydroxymethyl) ethyl acrylate, 2-chloro-1 -(Hydroxymethyl)
Examples thereof include ethyl methacrylate, 2-bromo-1- (hydroxymethyl) ethyl acrylate and 2-bromo-1- (hydroxymethyl) ethyl methacrylate.

[About component (B)] The component (B), t-butoxyalkyl (meth) acrylate consisting of mono (meth) acrylate as represented by the following general formula (I) is a 2-hydroxyalkyl (meth) acrylate. ) It can be obtained by adding isobutylene to acrylate.

[0023]

Embedded image

Since the component (B) has a low viscosity, it has a great effect of diluting the oligomer and has a good fast curing property.

Since the component (B) is a compound having a t-butyl group, the coating film obtained by curing the resin composition of the present invention comprising the compound and the component (A) has an appropriate hardness. In addition, it is possible to impart stain resistance and solvent resistance.

[Other Components] When ultraviolet rays are used as the active energy rays, one or more kinds selected from photopolymerization initiators, photosensitizers, photoaccelerators and the like are usually added to the composition of the present invention. It is preferable to include a photocatalyst compound.

Specific examples of the photopolymerization initiator include 2,2-
Dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthfluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoinpropyl ether, benzoinethyl ether, benzyldimethylketal, " 1
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-oxanthone, camphorquinone, 2-methyl-1- [4 (methylthio) phenyl] -2-morpholino-propane -1-one and the like can be mentioned.

A photopolymerization initiator having at least one acryloyl group or methacryloyl group in the molecule can also be used.

Examples of the photosensitizer include 2-chlorothioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone.

Specific examples of the light accelerator include ethyl P-dimethylaminobenzoate, isoamyl P-dimethylaminobenzoate, 2-n-butoxyethyl P-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. And so on.

The active energy ray-curable resin composition of the present invention may contain other radical-polymerizable vinyl-based monomer as long as the performance is not impaired.

The vinyl-based monomer can be appropriately selected and used from the compatibility with various known reactive oligomers and vinyl-based monomers.

The radical-polymerizable vinyl-based monomer is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-
Dicyclopentenoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, tetrahydrofur Furyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid, (meth)
Monofunctional (meth) acrylate monomers such as acryloylmorpholine acid, N-vinyl-2-pyrrolidone, N-vinylimidazole, N-vinylcaprolactam, styrene, α-methylstyrene, vinyltoluene, allyl acetate, vinyl acetate, vinyl propionate , Vinyl benzoate, and other vinyl monomers.

The resin composition of the present invention may contain an organic solvent in order to adjust it to a desired viscosity.

Examples of the organic solvent include ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate and methoxyethyl acetate; diethyl ether, ethylene glycol dimethyl ether, dioxane and the like. Examples thereof include ether compounds; aromatic compounds such as toluene and xylene; aliphatic compounds such as pentane and hexane; halogenated hydrocarbons such as methylene chloride, chlorobenzene and chloroform.

In the resin composition of the present invention, if necessary,
A polymerization inhibitor, a matting agent, a coloring pigment, a dye, a defoaming agent, a leveling agent, an antistatic agent, a dispersant, a plasticizer, a non-reactive polymer and the like can be added.

The resin composition of the present invention contains an ultraviolet ray, an electron beam,
Although it is cured by irradiation with active energy rays such as gamma rays, ultraviolet rays are particularly suitable, and examples of ultraviolet ray sources include solar rays, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, etc. Used.

[0038]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.

Further, "part" in the description means "part by weight" unless otherwise specified.

[Evaluation method] (1) Pencil hardness According to JIS K-5400 "pencil scratch test".

(2) Contamination resistance A 1 cm ² square was applied to the coating film with a marker, and after 24 hours, it was wiped off with ethanol-soaked gauze, and the degree of contamination remaining was evaluated on a five-point scale. The larger the number, the less the pollution.

(3) Solvent resistance The number of times until the substrate was exposed by rubbing the coating film with gauze soaked with methyl ethyl ketone (MEK) was shown.

[Synthesis Example 1] 400 parts of polyethylene glycol (average molecular weight 400), 666 parts of isophorone diisocyanate, 2-hydroxyethyl acrylate 46
Urethane acrylate A was obtained by reacting 4 parts at 60 ° C. for 10 hours.

[Example 1] Urethane acrylate A70
30 parts of 2-t-butoxyethyl acrylate and 3 parts of a photopolymerization initiator (manufactured by Nippon Ciba-Geigy; trade name Irgacure 184) were blended with the parts to prepare a resin composition.

The composition was applied to an acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd .; trade name: Acrylite) using a bar coater (# 60), and then a 80 W / cm high pressure mercury lamp (manufactured by Mitsubishi Rayon Engineering Co., Ltd.). ; Product name UV-
2503) Conveyor speed of 15 m / min.
The distance from the lamp was set to 20 cm, and the coating was repeatedly passed through until the coating became tack-free and UV-cured.

Table 1 shows the evaluation results of the cured film thus obtained.

[Example 2] Urethane acrylate A50
A cured coating film was obtained in the same manner as in Example 1 except that 50 parts of 2-t-butoxyethyl acrylate and 3 parts of a photoinitiator were added to the parts to prepare a resin composition. The evaluation results are shown in Table 1.

[Example 3] Urethane acrylate A30
70 parts of 2-t-butoxyethyl acrylate and 3 parts of a photopolymerization initiator were blended in 3 parts to prepare a resin composition to obtain a cured film. The evaluation results are shown in Table 1.

Examples 4 to 6 Cured coatings were obtained in the same manner as in Examples 1 to 3 except that 2-t-butoxypropyl acrylate was used instead of t-butoxyethyl acrylate. The evaluation results are shown in Table 1.

[Examples 7 to 9] Cured coatings were obtained in the same manner as in Examples 1 to 3 except that 2-t-butoxybutyl acrylate was used instead of t-butoxyethyl acrylate. The evaluation results are shown in Table 1.

[0051]

[Table 1]

Comparative Example 1 Urethane Acrylate A70
Except that 30 parts of 2-hydroxyethyl acrylate and 3 parts of a photopolymerization initiator are mixed in the above parts to prepare a resin composition.
A cured film was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Example 2 Urethane Acrylate A50
To 50 parts of 2-hydroxyethyl acrylate and 3 parts of a photopolymerization initiator to prepare a resin composition.
A cured film was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Example 3 Urethane Acrylate A30
Except that 70 parts of 2-hydroxyethyl acrylate and 3 parts of a photopolymerization initiator are mixed in the above parts to prepare a resin composition.
A cured film was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Example 4 Urethane Acrylate A70
A cured coating film was obtained in the same manner as in Example 1 except that 30 parts of 2-hydroxyhexyl acrylate and 3 parts of a photopolymerization initiator were added to each part to prepare a resin composition. The evaluation results are shown in Table 2.

Comparative Example 5 Urethane Acrylate A50
A cured coating film was obtained in the same manner as in Example 1, except that 50 parts of 2-hydroxyhexyl acrylate and 3 parts of a photopolymerization initiator were added to each part to prepare a resin composition. The evaluation results are shown in Table 2.

Comparative Example 6 Urethane Acrylate A30
Except that 70 parts of 2-hydroxyethyl acrylate and 3 parts of a photopolymerization initiator are mixed in the above parts to prepare a resin composition.
A cured film was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0058]

[Table 2]

[0059]

The active energy ray-curable resin composition of the present invention comprises a reactive oligomer having two or more (meth) acryloyl groups in the molecule of component (A) and a specific mono (meth) component of component (B). ) By combining with an acrylate, it is possible to form a cured film having a low viscosity and a fast curing property, and excellent in stain resistance and solvent resistance.

Claims (2)

[Claims] 1. A reactive oligomer having two or more (meth) acryloyl groups in the molecule as a component (A), and (B).
An active energy ray curable resin composition comprising a mono (meth) acrylate represented by the following general formula (I) as a component. Embedded image (In the formula, R ¹ represents H or CH ₃ , and R ² represents H, CH ₃ or CH ₂ CH _3. ) 2. As a component (A), 2 to 98 parts by weight of a reactive oligomer having two or more (meth) acryloyl groups in the molecule, and a mono (meth) represented by the general formula (I) as a component (B). The active energy ray-curable resin composition according to claim 1, which is a combination of 2 to 98 parts by weight of acrylate so as to be 100 parts by weight in total.