JP4457907B2 - Curable resin composition and use thereof - Google Patents

Description

  The present invention relates to a photocurable resin composition and an ink comprising the resin composition.

Conventionally, various resin compositions that are cured by light (such as ultraviolet rays) have been disclosed. Such resin compositions are used in inks, paints, adhesives, photoresists and the like.
For example, UV-curing type printing inks are highly evaluated for their high speed of curing and can be cured in a short time; they are environmentally friendly because they do not use solvents; It has spread. Conventionally, various combinations including ethylenically unsaturated compounds such as acrylate, photoinitiators, pigments and the like have been proposed as printing inks that are cured by ultraviolet rays.

  However, for example, an ink composition using dipentaerythritol hexaacrylate or the like as an ethylenically unsaturated compound has a storage stability of the ink composition itself, although it depends on the type of additive such as a photocuring agent to be added. It is generally known that it is not good. And in order to improve storage stability, the solution is achieved by adding a diallyl phthalate prepolymer (patent document 1).

  Also, for example, printing inks prepared using polyethylene glycol diacrylate as the ethylenically unsaturated compound have good fixing and fixing of the stamp ink on the dry film, but the printing ink alone has poor moisture resistance. It has been. And in order to improve moisture-proof water resistance, the solution is achieved by adding a diallyl phthalate prepolymer (patent document 2).

  As described above, a good effect is obtained by adding an inert resin typified by diallyl phthalate prepolymer. However, depending on the type of the ethylenically unsaturated compound that is the main component of the resin composition for printing ink, the solubility of the inert resin is poor, and the ink composition after addition becomes cloudy due to undissolved matter, The aptitude decreases. Conventional inert resins cannot be used depending on the type of ethylenically unsaturated compound.

  More specifically, in recent years, epoxidized soybean oil acrylate has been frequently used as an ethylenically unsaturated compound contained in an ink resin composition from the viewpoint of environmental protection. Epoxidized soybean oil acrylate is suitable for the environment because it is derived from plant components, but its solubility in diallyl phthalate prepolymer is poor, so white turbidity due to undissolved materials has been pointed out as a problem when preparing resin compositions. ing.

  As another example, there is a hybrid ink that has both printability and ease of handling, which are advantages of conventional oil-based inks, and that ultraviolet rays can be dried in a short time. The hybrid ink uses a relatively low polarity ethylenically unsaturated compound, so it has a printability similar to that of an oil-based ink although it is a photocurable ink. However, when a diallyl phthalate prepolymer is added, there is still a problem in solubility. .

JP-A-53-69706 JP-A-52-4310

  An object of the present invention is to provide a resin composition using a novel inert resin that can be used for a wide range of ethylenically unsaturated compounds, and more specifically, in an environment containing the above epoxidized soybean oil acrylate. An object of the present invention is to provide a resin composition having good solubility even when an inert resin typified by diallyl phthalate prepolymer is added to a gentle ink and a hybrid ink.

  As a result of various studies to solve the above problems, the present inventors comprise a compound (II) of a compound represented by the general formula (i) and a vinyl monomer (ii). When the prepolymer is used as an inert resin, the compatibility with the ethylenically unsaturated compound (I), which is the main component of the resin composition, is improved, and a wide range of resin compositions can be realized, and the present invention is completed. It came.

[ｎは１または２を表し、ＲはＨまたはＣＨ_３を表す。]
を含んでなる光硬化性樹脂組成物である。この場合、当該光照射により硬化可能なエチレン性不飽和化合物(I)と当該共重合物(II)から実質的になる当該光硬化性樹脂組成物が好ましい。
さらに、本発明は、当該光硬化性樹脂組成物を含んでなるインキおよび塗料である。この場合、当該光硬化性樹脂組成物から実質的になるインキおよび塗料が好ましい。 That is, the present invention
(I) an ethylenically unsaturated compound curable by light irradiation, and (II) a copolymer of a compound represented by the following formula (i) and a vinyl monomer (ii),

[n represents 1 or 2, and R represents H or CH ₃ . ]
Is a photocurable resin composition comprising In this case, the photocurable resin composition substantially consisting of the ethylenically unsaturated compound (I) and the copolymer (II) curable by the light irradiation is preferable.
Furthermore, this invention is the ink and coating material which comprise the said photocurable resin composition. In this case, an ink and a paint substantially consisting of the photocurable resin composition are preferable.

  Since the ethylenically unsaturated compound and the novel inert resin of the present invention are mixed in a wide range, the composition can be adjusted in a wide range suitable for the resin composition. In particular, in the case where propylene oxide-modified acrylate and epoxidized soybean oil acrylate coexist, it becomes possible to prepare a composition that cannot be realized by a conventional inert resin such as a dup prepolymer.

  Examples of the ethylenically unsaturated compound (I) used in the present invention include (meth) acrylic acid ester compounds, (meth) allyl compounds, and vinyl compounds. The ethylenically unsaturated compound may be a mixture of two or more compounds.

  Examples of (meth) acrylic acid ester compounds include pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, neopentyl glycol, 1,6-hexanediol, glycerin, polyethylene glycol, and polypropylene glycol. (Meth) acrylic acid ester compounds; those obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to these alcohols; (meth) acrylic acid ester compounds; bisphenols such as bisphenol A and bisphenol F, ethylene oxide, propylene oxide, etc. In addition to (meth) acrylic acid ester compounds with addition of alkylene oxide, epoxy (meth) acrylate, urethane (meth) acrylate Rate, alkyd (meth) acrylate, epoxidized soybean oil acrylate.

  Examples of (meth) allyl compounds include (meth) allyl ether compounds such as trimethylolpropane di (meth) allyl ether, pentaerythritol tri (meth) allyl ether, glycerin mono (meth) allyl ether, and acrylic acid (meth). There are (meth) allyl ester compounds such as allyl, di (meth) allyl maleate, and di (meth) allyl fumarate.

  Examples of the vinyl compound include styrene, or α-substituted styrene such as α-methylstyrene, α-ethylstyrene, α-chlorostyrene, and nucleus-substituted styrene such as fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene, and methoxystyrene.

A preferred ethylenically unsaturated compound (I) used in the present invention is a (meth) acrylic acid ester compound.
Further, it is preferable that epoxidized soybean oil acrylate is contained as a whole or a part of the ethylenically unsaturated compound (I). It is more preferable that epoxidized soybean oil acrylate is contained as a part of the ethylenically unsaturated compound (I). Most preferably, the epoxidized soybean oil acrylate occupies 1 to 20 parts by weight as a part of 100 parts by weight of the ethylenically unsaturated compound (I).

The copolymer (II) of the compound of the general formula (i) and the vinyl monomer (ii) is subjected to bulk polymerization at an appropriate temperature in the presence of an appropriate polymerization initiator such as a peroxide. Is obtained.
The preferred polymerization temperature is 80 to 200 ° C., and preferred peroxide initiators include benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-butyl peroxybenzoate, di-t-butyl peroxide, dicumyl peroxide. Etc. are exemplified.

In the compound (i), n is 1 or 2, R is H or CH ₃ , n is preferably 2, and R is preferably H. n of 2 means that Ar is a 1,2-, 1,3- or 1,4-phenylene group, and particularly preferred is a case where Ar is a 1,2-phenylene group. A mixture of two or more of these may be used.

The vinyl monomer (ii) copolymerizable with the compound of the general formula (i) may be monofunctional or polyfunctional. Two or more kinds of copolymerizable vinyl monomers can be used as a mixture, and there is no limitation on the mixing ratio, and any ratio can be selected. The weight ratio of the compound represented by the general formula (i) and the vinyl monomer (ii) is preferably (i) :( ii) = 99.9-50: 0.1-50, for example (i) :( ii) can be appropriately selected within the range of 99 to 70: 1 to 30. Select so that the sum of the numbers is 100
It is preferred to select the weight of the compounds (i) and (ii).

  Examples of such vinyl monomers include unsaturated esters, aromatic vinyl compounds, unsaturated fatty acids and derivatives thereof, unsaturated dibasic acids and derivatives thereof, and the like.

  Unsaturated esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) Alkyl (meth) acrylates such as acrylate, (iso) bornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) ) Acrylic aromatic esters such as acrylate and fluorophenyl (meth) acrylate, (meth) acrylic acid polyethylene glycol ester, (meth) acrylic acid polypropylene glycol ester, etc. It is done. Of these, (meth) acrylic acid polypropylene glycol ester is preferred.

  Examples of the aromatic vinyl compound include styrene, or α-substituted styrene such as α-methylstyrene, α-ethylstyrene, and α-chlorostyrene, and nucleus-substituted styrene such as fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene, and methoxystyrene.

  Examples of unsaturated fatty acids and their derivatives include unsaturated fatty acids and their derivatives, such as oleic acid, linoleic acid, linolenic acid, erucic acid, and alkyl esters thereof.

  Examples of unsaturated dibasic acids and derivatives thereof include maleic anhydride, fumaric acid, tetrahydrophthalic anhydride, and alkyl esters thereof.

  In addition to the monofunctional vinyl monomers as described above, examples of the vinyl monomers copolymerizable with the general formula (i) include crosslinkable polyfunctional monomers. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol Examples include di (meth) acrylates such as di (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. It is done.

  The weight average molecular weight of the copolymer (II) of the compound represented by the general formula (i) and the vinyl monomer (ii) is preferably in the range of 1,000 to 100,000, for example, 2,000 to 90,000. It may be. The softening point may preferably be in the range of 30 ° C to 200 ° C, such as 50 ° C to 180 ° C.

  The amount of the copolymer (II) added is preferably 5 to 60 parts by weight, for example 10 to 50 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound.

The resin composition according to the present invention can use a photopolymerization initiator for curing. Examples of photopolymerization initiators include 2-methyl-2-morpholino-1- [4- (methylthio) phenyl] -propan-1-one, acetophenones such as 1-hydroxycyclohexyl phenyl ketone, benzoin, and benzoin ethyl ether. Examples thereof include benzophenone series, benzophenone series such as benzophenone, phosphorus series such as acylphosphine oxide, sulfur series such as thioxanthone, and dibenzyl series such as benzyl and 9,10-phenanthrenequinone.
The amount of the photopolymerization initiator is preferably 20 parts by weight or less, for example, 0.5 to 15 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated compound.

  In curing, a photoinitiator (for example, an amine photoinitiator such as triethanolamine) can be used in combination with a photopolymerization initiator. The amount of the photoinitiator is preferably 20 parts by weight or less, for example, 0.5 to 10 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated compound.

The resin composition of the present invention includes various additives, for example, stabilizers (for example, polymerization inhibitors such as hydroquinone and methoquinone), colorants (for example, cyanine blue, disazo yellow, carmine 6b, Raked C, carbon black). In addition, pigments such as titanium white), other fillers, viscosity modifiers, and the like can be contained depending on the purpose.
The amount of the stabilizer is preferably 1 part by weight or less, for example, 0.001 to 0.5 part by weight based on 100 parts by weight of the ethylenically unsaturated compound. The amount of the colorant is preferably 100 parts by weight or less, for example, 5 to 80 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated compound.

  The resin composition of the present invention comprises an ethylenically unsaturated compound (I), a copolymer (II), and other photopolymerization initiators, photoinitiators, and additives (eg, stabilizers, pigments) as necessary. Can be prepared by mixing. The mixing method is not particularly limited, but it is preferable to mix the ethylenically unsaturated compound (I) and the copolymer (II) by heating and stirring, and then knead the additive with a three-roll mill.

  The resin composition of the present invention is cured by irradiation with light. The light to be irradiated can be appropriately selected depending on the type of curing agent to be used, but is usually cured by ultraviolet rays.

The use of the resin composition of the present invention is not particularly limited. Ink (for example, printing ink for photo-setting lithographic printing, silk screen ink, gravure ink, etc.), paint (for example, paper, plastic, metal, woodwork, etc., for example, overprint varnish ), Adhesives, photoresists and the like. As a paint, use as an overprint varnish is preferable.
The resin composition of the present invention exhibits its effect sufficiently if included in the application, but the application consisting essentially of the resin composition is desirable.

For example, a general method for producing ink is as follows.
The copolymer (II) is preferably dissolved in the ethylenically unsaturated compound (I) with stirring at a temperature of 40 ° C. to 140 ° C., and if necessary, a stabilizer (especially polymerization of hydroquinone, methoquinone, etc.). Inhibitors) and / or photoinitiators are added to obtain a mixture. An ink can be obtained by adding a pigment to the mixture.
The overprint varnish can be produced by the same procedure as that for the ink except that no pigment is used.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
[Production Example 1]
Manufacture of diallyl phthalate and dipropylene glycol acrylate copolymer 95 liters of diallyl phthalate monomer (Daiso Co., Ltd .; Daiso Dup Monomer) and 5 g of methoxydipropylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd .; DPM- A) Place in flask and blow with nitrogen gas replacement. Thereafter, the temperature is raised to 160 ° C., and stirring is performed while adding 0.4 g of perbutyl D (manufactured by NOF Corporation, di-t-butyl peroxide) as a polymerization initiator. After cooling, the polymerization solution is placed in about 10 times the amount of methanol and stirred vigorously. The white solid precipitated was filtered and dried to obtain a prepolymer. The weight average molecular weight of this prepolymer was about 25000. The weight average molecular weight was measured by GPC analysis using standard polystyrene as a standard. For GPC measurement, Showa Denko GPC columns, KF806, 804, 803, 802, 801 were used. Tetrahydrofuran was used as the eluent, and a UV detector (wavelength 254 nm) was used as the detector.

[Examples 1-3, Comparative Examples 1-3]
Based on the composition of Table 1, Examples 1 and 3 and Comparative Examples 1 and 3 were mixed at a temperature of 120 ° C. in a 100 ml glass container so that the total amount was about 50 g, to obtain a composition. It was.
In Example 2 and Comparative Example 2, the components other than the epoxidized soybean oil acrylate were mixed in a 100 ml glass container at a temperature of 120 ° C., cooled to room temperature, and then added with epoxidized soybean oil acrylate and stirred. Got.

(Solubility)
Each composition obtained by Examples 1-3 and Comparative Examples 1-3 was cooled to room temperature (25 degreeC), and the state after standing for 24 hours was confirmed visually.
As a result, when the ethylenically unsaturated compound (I) having a relatively high polarity is used, there is no significant difference in solubility from when the diallyl phthalate prepolymer is used as the inert resin (Example 3 and comparison). Example 3) When the ethylenically unsaturated compound (I) having a low polarity was used, there was a significant difference in solubility between the two (Examples 1 and 2 and Comparative Examples 1 and 2).
○: dissolution, transparent ×: cloudiness

ジアリルフタレートプレポリマー：ダイソー（株）製、ダイソーダップＡ
３ｍｏｌＰＯ変性トリメチロールプロパントリアクリレート：サートマー カンパニー（Ｓａｒｔｏｍｅｒ Ｃｏｍｐａｎｙ）製、ＳＲ４９２
トリメチロールプロパントリアクリレート：共栄社化学（株）製、ＴＭＰ−Ａ
エポキシ化大豆油アクリレート：サートマー カンパニー（Ｓａｒｔｏｍｅｒ Ｃｏｍｐａｎｙ）製、ＣＮ１１１
ハイドロキノン：片山化学工業（株）製、試薬特級

Diallyl phthalate prepolymer: Daiso Dup A, manufactured by Daiso Corporation
3 mol PO-modified trimethylolpropane triacrylate: SR492 manufactured by Sartomer Company
Trimethylolpropane triacrylate: manufactured by Kyoeisha Chemical Co., Ltd., TMP-A
Epoxidized soybean oil acrylate: CN111 manufactured by Sartomer Company
Hydroquinone: Made by Katayama Chemical Co., Ltd., reagent grade

[Examples 4 to 6 and Comparative Example 4]
Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd .; 2-methyl-2-morpholino-1- [4- (methylthio) phenyl] -propane- was added to 97 parts by weight of the composition prepared in Examples 1 to 3 and Comparative Example 3. 1-on) Overprint varnish (hereinafter referred to as OP varnish) was prepared by adding 3 parts by weight.

(UV curable)
These OP varnishes were coated on art paper (manufactured by Oji Paper Co., Ltd., one side of Kinto) using an RI tester, and irradiated with ultraviolet rays at a conveyor speed of 10 m / min with a 120 W / cm halogen lamp. The presence or absence of tack was examined by touch.
As a result, the resin composition according to the present invention showed the same curability as the conventional product.
○: No tack ×: Tack

(Pencil hardness)
The hardness of the cured films obtained by coating the OP varnishes of Examples 1 to 3 and Comparative Example 4 on a glass plate and irradiating them with ultraviolet rays at a conveyor speed of 5 m / min with a 120 W / cm halogen lamp was measured according to JIS K- 5600-5-4: It measured based on 1999.
As a result, the resin composition according to the present invention showed the same curability as the conventional product.

[Example 7]
An ink composition was prepared by adding 4 wt% of Irgacure 907 (manufactured by Ciba Specialty Chemicals) and 20 wt% of cyanine blue to 76 wt% of the composition prepared in Example 1. The obtained ink composition was printed and irradiated with ultraviolet rays at a conveyor speed of 10 m / min using a 120 W / cm halogen lamp, a good cured coating film could be obtained.

[Example 8]
Using the composition prepared in Example 2, the same operation as in Example 6 was performed to prepare an ink composition, which was printed and irradiated with ultraviolet rays. As a result, a good cured coating film could be obtained.

  INDUSTRIAL APPLICABILITY The present invention can be effectively used in the field of manufacturing inks, paints, and the like, and in the field of manufacturing resin compositions involved in supplying raw materials.

Claims (5)

Selected from the group of pentaerythritol, dipentaerythritol, trimethylolpropane, (meth) acrylic acid ester compounds of ditrimethylolpropane, and (meth) acrylic acid ester compounds obtained by adding ethylene oxide or propylene oxide to these alcohols A copolymer of at least one compound (I) and a compound represented by the following formula (i) with (meth) acrylic acid triethylene glycol ester or (meth) acrylic acid dipropylene glycol ester (ii) ( II),

[ n represents 2 and R represents H or CH ₃ . Ar represents a 1,2-, 1,3- or 1,4-phenylene group. ]
A photocurable resin composition comprising: The resin composition according to claim 1 , further comprising epoxidized soybean oil acrylate. An ink comprising the resin composition according to claim 1 . The coating material containing the resin composition in any one of Claims 1-3 . The paint according to claim 4 , which is an overprint varnish.