JPS60133003A - Resin composition curable by active energy ray - Google Patents

Abstract

PURPOSE:A composition having improved dispersibility of pigment, improved printability and coating performances, curable by radiation such as electron rays, etc., containing a copolymer of diallyl phthalate and a vinyl compound, a vinyl monomer, etc. CONSTITUTION:(A) A copolymer of (i) diallyl phthalate and/or a polymer blended with diallyl phthalate and (ii) a vinyl compound [e.g., 6-18C alkyl-containing lactone modified (meth)acrylate, etc.] is blended with (B) a vinyl monomer [e.g., (meth)acrylic acid ethyl ester, triacryl isocyanurate, etc.] and/or prepolymer in a blending ratio of preferably 5-50pts.wt. component A to 95-50pts.wt. component B. The copolymer of the component A is preferably prepared by reacting 100pts.wt. component i with 5-50pts.wt. component ii in the presence of a radical generator.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a resin composition that can be cured by radiation such as ultraviolet rays or electron beams and has excellent printability and paintability. A composition that forms a cured coating film by radiation irradiation is a solvent-free coating composition that can rapidly cure the coating film at room temperature instead of one that is polymerized by heat, eliminating pollution problems, especially air pollution caused by solvents. As such, research is being actively conducted, and practical application is progressing in the fields of printing inks, paints, etc. These are radical polymerizable monomers and prepolymers having radical polymerizability, and if necessary, a radical polymerization initiator.

It consists of pigments and other additives, and the prepolymers include alkyd acrylate, polyester acrylate, epoxy acrylate, urethane acrylate, etc., and the monomers include bisphenol A alkylene oxide adduct diacrylate neopentyl glycol diacrylate, trimethylolpropane triacrylate, etc. Acrylate.

Tetramethylolmethanetetraacrylate, dipentaerythritol hexaacrylate, alkylphenol alkylene oxide adduct monoacrylate, and the like have been used.

However, these prepolymers have poor pigment dispersibility;
Printing ink For example, when using offset printing ink,
The fluidity was poor and there were problems with printability. To improve these properties.

Although a diallyl phthalate prepolymer was used.

(Japanese Unexamined Patent Publication No. 51-143468), it could not be said that fluidity was sufficiently improved when combined with certain pigments.

The present inventors have conducted intensive research to solve the above problems, and as a result, they have found excellent R material dispersibility and fluidity. We have discovered an active energy ray-curable resin composition. That is, the present inventor has developed an active energy ray-curable resin containing a copolymer (A) of diallyl phthalate and/or diallyl phthalate prepolymer and a vinyl compound, and a vinyl monomer and/or prepolymer [B]. It is a composition.

In the present invention, the copolymer (A) is synthesized from a diallyl phthalate prepolymer such as diallyl orthophthalate or diallyl isophthalate or a polymer thereof, and a vinyl compound. As vinyl compounds, acrylic esters and methacrylic esters having an alkyl group, an amino group, a silane group, etc. are effective, and those containing an alkyl group include methyl, ethyl, n-propyl, and isopropyl.

n-butyl, iso-butyl, 5ec-butyl, 1-butyl, n-amyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, n-hexyl, 2-methyl-1- Pentyl, 2-ethyl-1-butyl, 5e
c-amyl, t-amyl, 4-methyl-2-pentyl,
n-heptyl, 2-heptyl, n-octyl, 2-ethyl-1-hexyl.

2-octyl, n-nonyl, n-decyl, 5-ethyl-
2-nonyl, n-dodecyl, n-tetradecyl, 2-methyl-7-ethyl-4-undecyl.

Acrylic esters and methacrylic esters of n-hexadecyl and stearyl, preferably having 6 to 1 carbon atoms.
A lactone-modified acrylate monomer (trade name Plaxel), which is an acrylic ester modified with an acrylic acid alkyl ester or methacrylic acid alkyl ester having 8 long-chain alkyl groups and a lactone compound to introduce a polyester bond with a degree of polymerization of 2 to 4 into the molecule. (manufactured by Daicel Chemical Industries, Ltd.), TClIO3, TCj20s (manufactured by Nippon Kayaku ■)). Those containing amide or amino groups include acrylamide, methacrylamide, 2-aminoethyl vinyl ether, N-methylolacrylamide, ureido vinyl ether, ureido ethyl acrylate, etc. Those containing silane groups include vinyltrimethoxysilane, vinyltriethoxysilane, Tetravinylsilane, γ-methacryloxypropyltrimethoxysilane.

α-trimethylsilylacrylic acid, vinyltrimethylsilane, etc.

The copolymer (A) can be obtained by reacting 100 parts by weight of diallyl phthalate or diallyl phthalate prepolymer with 5 to 50 parts by weight of a vinyl compound, preferably in a solvent solution in the presence of a radical generator.

As the vinyl monomer and/or the vinyl monomer in the prepolymer CB) in the present invention.

Acrylic acid, methacrylic acid, or esters thereof are not particularly limited as long as they are addition polymerizable.

For example, esters of polyhydric alcohols and acrylic acid and/or methacrylic acid, such as ethyl (meth)acrylate, butyl (meth)acrylate 5, and 2-ethylhexyl (meth)acrylate.

Ethylene glycol di(meth)acrylate, 1゜6-
Hexadecyl diol di(meth)acrylate 1,3-butanediol di(meth)acrylate.

Trimethylolpropane (meth)acrylate.

Pentaerythritol di(meth)acrylate.

Pentaerythritol tri(meth)acrylate.

dipentaerythritol hexa(meth)acrylate,
dipentaerythritol penta(meth)acrylate,
Examples include triacrylisocyanurate and vinylpyrrolidone. In addition, conventionally known prepolymers can be used, including reaction products of a resin synthesized from bisphenol A and epichlorohydrin and acrylic acid and/or methacrylic acid, and dicarboxylic acids such as phthalic acid and hexahydrophthalic acid. Reaction products of resins synthesized from epichlorohydrin and acrylic acid/methacrylic acid, fatty acid modification reaction products with excess hydroxyl groups, unsaturated polyesters, allyl alcohols that share hydroxyl groups and ethylenically unsaturated bonds, butyne diol, β - A resin obtained by esterifying acrylic acid and/or methacrylic acid with a resin having a hydroxyl group obtained by a copolymerization reaction of bitroxyl acrylate or the like and dicyclopentadiene is used.

゛Photopolymerization initiators used in the present invention include benzoin 5-benzoin methyl ether, benzoin isopropyl ether, and benzophenone.

0-Methylbenzoylbenzoic acid ester, benzyl, 2
-Chlorthioxanthone, 2,2-dichloroacetophenone, 2,2-dichloro-4-hydroxyacetophenone, acetophenone, p-chlorobenzophenone, anthraquinone, 2-ethylanthraquinone, and the like.

In the present invention, the blending ratio of the copolymer (A) and the vinyl monomer and/or prepolymer CB) is (A) 5
CB) 95 to 50 parts by weight.

The active energy ray-curable resin composition of the present invention may optionally contain other resins 2, such as epoxy resins.

Pigments and dyes such as acrylic resin and polyester resin.

Various additives, stabilizers, etc. can be added.

It can be applied to a wide range of applications such as printing ink and paint.

The present invention will be explained below with reference to Examples. All parts in the examples indicate parts by weight.

Synthesis Example 1 (Synthesis of Copolymer (A)) Heat to 80° C. in a di-atmosphere in a reactor equipped with a reflux condenser and a stirrer. This includes stearyl acrylate, 4.59
19 parts of benzoyl peroxide and 24.56 parts of methyl ethyl ketone were added dropwise little by little over 30 minutes while stirring and maintaining the temperature at 80'C. One hour after the completion of the dropwise addition, 0.2 part of hydroquinone was added, and methyl ethyl ketone was removed under reduced pressure to obtain resin (2).

Synthesis Example 2 (Synthesis of Copolymer (A)) Using the same apparatus as in Synthesis Example 1, heat to diallyl ortho 0°C.

To this, 1.54 parts of N-methylolacrylamide, α,
Mixture of 0.19 parts of αazobisisobutyronitrile and 21.5 parts of methyl ethyl ketone/8? &, were added dropwise in the same manner as in Synthesis Example 1, and methyl ethyl ketone was distilled under reduced pressure to obtain resin (2).

Synthesis Example 3 (Synthesis of Copolymer (A)) Using the same apparatus as in Synthesis Example 1, heating was performed with diallyl osoph. To this, γ-methacryloxypropyltrimethoxysilane 3.6
A mixed solution of 3 parts of benzoyl peroxide, 0.2 parts of benzoyl peroxide, and 23.57 parts of methyl ethyl ketone was added dropwise in the same manner as in Synthesis Example 1, and methyl ethyl ketone was distilled under reduced pressure to obtain resin (2).

Synthesis Example 4 (Synthesis of Copolymer (A)) Using the same apparatus as in Synthesis Example 1, heat to diallyl ortho. To this, Plaxel FA-3 (manufactured by Daicel Chemical Industries ALL) 1
A mixed solution of 2.0 parts of benzoyl peroxide, 0.2 parts of benzoyl peroxide, and 22.0 parts of methyl ethyl ketone was added dropwise in the same manner as in Synthesis Example 1.
Methyl ethyl ketone was distilled under reduced pressure to obtain resin (2).

Example 1 030 parts of the resin obtained in Synthesis Example 1 was converted to dipentaerythritol hexaacrylate (hereinafter abbreviated as DPHA) 70 parts.
The mixture was melted at the same time to obtain varnish ■. Similarly, varnish ■ is better than resin ■, and varnish ■ is better than resin ■.

Varnish ■ is better than resin ■, and Diazi is used as a comparative example.

D P 11 30 parts of fluorothophthalate prepolymer
Varnish (■) was obtained by dissolving with 70 parts of A.

Next, offset inks of each color in the process were manufactured using each of the above varnishes. The ink formulation is shown below.

Blue ink formulation: Lionol Blue G (Toyo Ink Manufacturing II M) 2
0 parts・talc 5・varnish 45・benzophenone 5・photopolymerization 1! J4 ・A −B P E −420.5 ・Hydroquinone 0.5 Bisbuenol A ethylene oxide adducted acrylate, (manufactured by Shin Nakamura Chemical ■) Red ink formulation ・Sumikaprint Carmine 6B (manufactured by Sumitomo Chemical ■) 18 parts ・Talc 5 - Varnish 39 - Hengeine ethyl ether 5 - Photopolymerization accelerator, 4 - A-B PE-428,5 - Hydroquinone 0.5 Yellow ink formulation - Lionol Yellow FG (manufactured by Toyo Ink Manufacturing ■) 13
．． 5 parts - Alumina white 6 - Talc 5 - Varnish 40 - Benzophenone 5 - Photopolymerization accelerator 4 - A-B PE -426.0 - Hydroquinone 0.5 Gold red ink formulation - Lake Red C toner No., 50 23 parts・Aerosil 2 ・Hensifenone 5 ・Varnish 30 ・Photopolymerization accelerator 4 ・DPHA 15 ・A-B PE-420,5 ・Hydroquinone 0.5 Black ink formulation ・Mitsubishi Carbon MA-7 (manufactured by Mitsubishi Chemical 01) 9 parts・Lionol Bioresoto R (manufactured by Toyo Ink Manufacturing 111)
■ - Lionol Blue P (manufactured by Toyo Ink Manufacturing @1) - Alumina White 3 - Benzophenone 5 - Varnish 40 - Photopolymerization accelerator 4 - D P HA 34.5 - High 1' Rokinone 0.5 Manufactured with the above recipe Using a parallel plate viscometer (spread meter), the temporal changes in the ink spread radius (mm) of five types of indigo inks using varnishes ■ to ■ were measured and plotted on one-piece logarithmic coordinates.

The difference between the measurements at 20 seconds and 90 seconds indicates the flow slope (Figure 1). Other inks were measured using the same procedure, and the flow slopes are shown in Table 1.

As is clear from Table 1, it can be seen that the off-cent printing inks using varnishes (1) to (2) according to the present invention have a larger flow slope and superior fluidity than varnish (1) according to the comparative example.

Next, each of the above color inks was printed on carton paper using an R1 tester and irradiated with ultraviolet light using a 2KW ozone-less high pressure mercury lamp at an irradiation power of 1ilt 10cm and a line speed of 8.4m/min. A cured film was obtained with one irradiation.

Table 1 Flow slope

[Brief explanation of the drawing]

FIG. 1 is a graph showing temporal changes in the spreading radius of Offsen 1 printing indigo ink using varnishes 1 to 2, measured by a parallel plate viscometer. Patent Applicant Toyo Ink Mfg. Co., Ltd. 1st Figure Procedural Amendment (Method) % Formula % ■, Incident Indication Patent Application No. 239925, 1982
,〉3Mei name Active energy ray curable resin composition 3
, Relationship with the case of the person making the amendment Patent applicant

Claims (1)

[Claims] 1. A copolymer of diallyl phthalate and/or diallyl phthalate prepolymer and a vinyl compound (A
) and vinyl monomer and or prepolymer CB
) An active energy ray-curable resin composition comprising: 2. The active energy ray-curable resin composition according to claim 1, wherein the vinyl compound is at least one selected from acrylic esters and methacrylic esters. 3. The active energy ray-curable resin composition according to claim 2, wherein the acrylic ester or methacrylic ester has an alkyl group having 6 to 18 carbon atoms. 4. The active energy ray-curable resin composition according to claim 2, wherein the acrylic acid ester or methacrylic ester is a rough-modified acrylate or methacrylate.