JPH0718042A - Diluent for photopolymerizable resin and photopolymerizable resin composition - Google Patents

Abstract

PURPOSE:To obtain the diluent having low visocity, being lowly irritating to the skin, having a high curing rate, and being capable of providing a cured product improved in adhesion and flexibility and to provide the composition containing the diluent. CONSTITUTION:The diluent comprises a polyosyethylene/polyosypropylene block copolymer diacrylate or dimethacrylate, and ratio of the average number of moles of the polyoxyethylene groups added to that of the polyoxypropylene groups added is (0.1-1):1, with the sum of the average numbers of moles of addition being 20-46. The composition comprises 5-90wt.% polyoxyethylene/ polyoxy-propylene block copolymer (meth)acrylate, 5-90wt.% at least one oligomer selected from among a urethane (meth)-acrylate, an epoxy resin (meth) acrylate and a polyester (meth)acrylate, and 1-8wt.% photopolymerization initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable resin diluent, and further to a photopolymerizable resin composition using the same.

[0002]

2. Description of the Related Art Conventionally, acrylic acid ester or methacrylic acid ester (hereinafter referred to as "diluent for photopolymerizable resin")
(Acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid), and examples thereof include phenoxyethyl acrylate, phenoxypolyoxyethylene acrylate, ethylcarbitol acrylate, tetrahydrofurfuryl acrylate, polyoxyethylene mono (meth) acrylate, and polyoxyethylene mono (meth) acrylate. Oxypropylene mono (meta)
Mono (meth) acrylates such as acrylate: 1,6
-Hexanediol diacrylate, 1,9-nonanediol diacrylate, polyoxyethylene di (meth)
Di (meth) acrylates such as acrylate, polyoxypropylene glycol di (meth) acrylate, polyoxyethylene bisphenol A di (meth) acrylate: polyfunctional such as trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate Acrylate is an example.

However, these (meth) acrylic acid esters have the properties required as a diluent for photopolymerizable resins, namely, a high curing rate, a low viscosity, and adhesion and flexibility as properties after curing. None of them satisfy these many characteristics such as excellent flexibility and low skin irritation. For example, JP-A-3-6664
No. 3, the compound, that is, a glycol component such as 2,2,4-trimethyl-1,3-pentanediol, 2,2-diethyl-1,3-propanediol or an alkylene oxide adduct thereof ( The (meth) acrylic acid ester has no problem in terms of curing speed and skin irritation, but has a problem in adhesion and flexibility between the cured resin and the substrate.

Furthermore, the polyoxyethylene di (meth) acrylates disclosed in JP-A-4-33968 and JP-A-60-248400 have a problem in flexibility after curing, and polyoxypropylene di (meth) acrylate has a problem. (Meth) acrylate had a problem in adhesion after curing.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a photopolymerizable resin having a low viscosity, a low skin irritation, a high curing rate by visible light and ultraviolet rays, and an improved adhesion and flexibility of a cured product. A diluent for use is provided. Furthermore, the present invention provides a photopolymerizable resin composition using the same.

[0006]

The present invention comprises a di (meth) acrylic acid ester of a polyoxyethylene polyoxypropylene block copolymer, wherein the ratio of the average number of moles of polyoxyethylene groups and polyoxypropylene groups added is Is 0.1 to 1: 1 and the total number of added moles is 2
It is a diluent for photopolymerizable resin of 0 to 46.

The present invention further provides (A) 5 to 90% by weight of a diluent for a photopolymerizable resin according to claim 1, (B) urethane (meth) acrylate, epoxy resin (meth) acrylate or polyester (meth) acrylate. A photopolymerizable resin composition comprising 5 to 90% by weight of one or more oligomers selected from the following and 1 to 8% by weight of (C) a photopolymerization initiator.

The diluent for photopolymerizable resin which is a di (meth) acrylic acid ester of the polyoxyethylene-polyoxypropylene block copolymer of the present invention will be described below. The polyoxyethylene polyoxypropylene block copolymer portion is a block copolymer of propylene oxide and ethylene oxide, and the order of the polyoxyethylene group and the polyoxypropylene group and the number of blocks are not limited. Further, the ratio of the total average addition mole number of polyoxyethylene groups to the total average addition mole number of polyoxypropylene groups is 0.1 to 1: 1. At this time, if the ratio of the total average number of added moles of polyoxyethylene groups is less than 0.1, the adhesion between the cured resin and the substrate becomes poor, and the skin irritation becomes insufficient. When the ratio of the total average added mole number of polyoxyethylene groups exceeds 1, the curing rate in visible light, ultraviolet rays, etc. is remarkably slowed, and the flexibility of the cured product is not obtained. If the total of the average number of added moles of the polyoxyethylene-polyoxypropylene block copolymer portion is less than 20, the adhesion is insufficient and the skin irritation is strong. If the total of the average number of added moles exceeds 46, the curing rate will be slow, and the flexibility of the cured product will not be obtained.

The polyoxyethylene-polyoxypropylene block copolymer portion is obtained by the addition reaction of ethylene oxide and propylene oxide to ethylene glycol in this order, or propylene oxide and ethylene oxide to propylene glycol in this order.

The esterification reaction between the polyoxyethylene polyoxypropylene block copolymer and (meth) acrylic acid is also carried out according to a conventional method. The charging equivalent ratio (COOH / OH) of the carboxyl group and the alcoholic hydroxyl group in the charging raw material is 1 or more, preferably 1.1 to 1.
It is 5.

The photopolymerizable resin composition containing the photopolymerizable resin diluent of the present invention in combination with an oligomer and a photopolymerization initiator is cured by irradiation with visible light or ultraviolet light. Examples of the oligomer include urethane (meth) acrylate obtained by reacting urethane obtained from diisocyanate and diol with (meth) acrylic acid; epoxy resin (meth) composed of epoxy resin and (meth) acrylic acid Acrylate: Polyester (meth) acrylate obtained by reacting polyester obtained from polybasic acid or polyhydric alcohol with (meth) acrylic acid.

The composition of the photopolymerizable resin composition of the present invention comprises 5 to 90% by weight of a diluent for a photopolymerizable resin and an oligomer.
It is preferably 30 to 70% by weight, and 1 to 8% by weight as a photopolymerization initiator.

Polyoxyethylene polyoxypropylene block copolymer (meth) which is a diluent for photopolymerizable resin
If the amount of acrylic acid ester is less than 5% by weight, the adhesion between the cured resin and the substrate will be poor, and if it is more than 90% by weight, the flexibility will be poor. If the amount of the oligomer is less than 5% by weight, the flexibility becomes poor, and if it is more than 90% by weight, the viscosity of the photopolymerizable resin composition becomes high, which is not preferable.
If the amount of the photopolymerization initiator is less than 1% by weight, the curing is insufficient, and if it is more than 8% by weight, a remarkable effect cannot be obtained.

Examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one,
Acetophenone derivatives such as 1-hydroxycyclohexyl phenyl ketone; benzoin derivatives such as benzoin and benzoin isopropyl ether; benzophenone derivatives such as benzophenone and 4-phenylbenzophenone; and thioxanthone derivatives such as thioxanthone and isopropylthioxanthone.

Pigments and dyes may be further added to the photopolymerizable resin composition of the present invention.

Further, the diluent for photopolymerizable resin of the present invention is
It can also be used in a curing method using an electron beam, a laser beam, an X-ray, etc. in addition to visible light and ultraviolet rays.

The photopolymerizable resin diluent and photopolymerizable resin composition of the present invention are UV curable paints (UV top coats for woodworking, vinyl floor coats, overprint varnishes for paper, optical fiber coats, etc.), Printing inks for planographic printing, printing inks for letterpress, printing inks for intaglio, printing inks for stencil, UV curing adhesives, UV curing adhesives, adhesives for electronic parts, photo-molding sheets, liquid crystal color filters, dry film resists, semiconductors Resist, CRT protection coat, IC sealant, IC protection coat, solder resist,
It can be used as an electrodeposition resist, a masking resist, a PS plate photosensitive material, a printing plate substrate resin, and the like.

[0018]

The photopolymerizable resin diluent of the present invention has a low viscosity, a low skin irritation and a high curing rate, and a photopolymerization using the photopolymerizable resin diluent of the present invention. The resin composition exhibits excellent adhesiveness and flexibility to the base material of the cured product.

[0019]

The present invention will be described below with reference to examples. In the examples,% is based on weight. Synthesis Example Propylene glycol was sequentially subjected to addition reaction of propylene oxide and ethylene oxide to obtain a glycol of polyoxyethylene-polyoxypropylene block copolymer, and then acrylic acid or methacrylic acid was reacted to give No. 1 in Table 1. 1-No. A pale yellow diluent for photopolymerizable resin consisting of the diester of 6 was obtained.

[0020]

[Table 1]

No. 1 in Table 1 was obtained by reacting the monomethacrylic acid ester of the polyoxyethylene polyoxypropylene block copolymer with methacrylic acid chloride. 7
A diluent for photopolymerizable resin consisting of the diester shown in was obtained. In addition, No. 1-No. The diluting agent for photopolymerizable resin of No. 6 has a polyoxypropylene group at the center of the polyalkylene glycol and a polyoxyethylene group at the end, and N
o. 7 has both a polyoxyethylene group and a polyoxypropylene group at the end.

Examples 1 to 5 and Comparative Examples 1 to 6 Resin compositions obtained by blending a diluent for a photopolymerizable resin, an oligomer and a photopolymerization initiator with the compositions shown in Table 2 were coated on various substrates. It was applied to a thickness of 20 μm with a coater. Then, it was passed through a position of 8 cm under a metal halide lamp (80 W / cm, 1 lamp) to carry out curing, and the curing rate, adhesion and flexibility were measured. The results are shown in Table 3. For the diluent for photopolymerizable resin, see P. I. I. The (primary skin irritation index) was measured, and the measurement results are shown in Table 2.

[0023]

[Table 2]

[0024]

[Table 3]

The above test methods are shown below. (1) P. I. I. (Primary skin irritation index) measuring method: Draize method (Draze method (J.Pharm. & Exp.Ther. 82,337 (19
44))). That is, a sample solution of a diluent for a photopolymerizable resin was applied to the skin of the back of a rabbit, which had been shaved, and the symptom was observed after a certain period of time, and the skin irritation was evaluated based on the state of redness.

(2) Curing speed test: A resin composition having the composition shown in Table 2 was applied onto an aluminum plate, and a position of 8 cm under a metal halide lamp (80 W / cm, 1 lamp) was conveyed at a conveyor speed of 1 to 20 m / min. During this period, the speed was changed every 1 m / min for curing. Then, the cured product was scraped off and the infrared absorption spectrum was measured by the tablet method to give 164
The maximum value of the conveyor speed at which the absorption of the polymerizable ethylene group at 0 to 1650 cm -1 disappeared was expressed as the curing rate.

(3) Adhesion test: A resin composition having the composition shown in Table 2 was applied on an aluminum plate, an acrylic resin plate, a vinyl chloride resin plate, and a polycarbonate plate, respectively, and under a metal halide lamp (80 W / cm, 1 lamp). The position of 8 cm was moved at a conveyor speed of 2 m / min to cure. Then, JIS K 5400 8.2-199
The test was carried out by the method of 0 grid. That is, a 10 × 10 cross-cut was made on the coated surface with a cutter knife at 1 mm intervals, and cellophane tape was adhered to the surface and then peeled off to evaluate the adhesiveness.

(4) Flexibility test: Evaluation was made by the following two methods. 1) Erichsen test method: Erichsen test method (JIS K
5400 8.2-1990), a test piece was prepared by coating an aluminum plate having a thickness of 1 mm and a width of 70 mm with the resin composition shown in Table 2 and curing the composition by irradiating with an ultraviolet ray using an Erichsen tester. The punch was pushed into the center of the width from the back surface at a speed of 15 mm / min, and the distance traveled by the tip of the punch at the time when a crack was formed in at least one location of the test piece was expressed as an Erichsen value (mm).

2) Bending Property Test: (Bending Resistance Test) JIS K 5400 8.1 was used by using a test piece obtained by coating a steel sheet with the resin composition shown in Table 2 and curing it by irradiation with ultraviolet rays.
According to the method of -1990, the test piece was bent 180 degrees to show its surface state.

As is clear from Tables 2 and 3, the diluent for photopolymerizable resin of the present invention is the conventionally known 2,2-diethyl-1,3-propanediol ethylene oxide 4 of Comparative Example 1. A diacrylate of a mole addition product, or (meth) such as phenoxyethyl acrylate of Comparative Example 4
Skin irritation is lower than that of acrylic acid ester, and further, skin irritation is compared to that of the (meth) acrylic acid ester of Comparative Example 2 in which the ratio of polyoxyethylene group to polyoxypropylene group is outside the scope of the present invention. It is not very popular. Further, the photopolymerizable resin composition using the diluent for the photopolymerizable resin of the present invention,
Compared to Comparative Examples 2 and 3 in which the ratio of polyoxyethylene groups to polyoxypropylene groups and the total number of average added moles are outside the scope of the present invention, the cured product has excellent adhesion to the substrate and flexibility. ing.

Claims (2)

[Claims] 1. A polyoxyethylene polyoxypropylene block copolymer comprising a diacrylate ester or a dimethacrylate ester, wherein the ratio of the average number of added moles of the polyoxyethylene group and the polyoxypropylene group is 0.1 to 0.1.
1: 1 and the total number of average added moles is 20 to 46
Is a diluent for photopolymerizable resin. 2. A selected from (A) 5 to 90% by weight of the diluent for photopolymerizable resin according to claim 1, (B) urethane acrylate, urethane methacrylate, epoxy resin acrylate, epoxy resin methacrylate, polyester acrylate or polyester methacrylate. A photopolymerizable resin composition comprising 5 to 90% by weight of one or more oligomers and 1 to 8% by weight of (C) a photopolymerization initiator.