JPS58204060A - Photosensitive coating material - Google Patents

Abstract

PURPOSE:To provide a photosensitive resin compsn. having excellent corrosion resistance and adhesion to metal as well as good resistance to heat and chemicals, by adding a photoinitiator, an unsaturated silane compd., an unsaturated phosphate ester and a corrosion inhibitor to a photocuring component consisting of a prepolymer and a monomer, each of the prepolymer and the monomer having ethylenically unsaturated group. CONSTITUTION:0.2-10pts.wt. photoinitiator, 0.1-3pts.wt. unsaturated silane compd. such as vinyl-trimethoxysilane, 0.2-5pts.wt. unsaturated phosphate ester such as mono (2-methacryloxyethyl) phosphate and 1-30wt% (based on the amount of the phosphate ester) 2,4-diamino-6-phenyl-1,3,5-triazine are blended with 100pts.wt. photocuring component consisting of an epoxy (meth)-acrylate type prepolymer (or ester (meth)-acrylate type prepolymer) or urethane acrylate type prepolymer having ethylenically unsaturated groups at both terminals and a monomer having an ethylenically unsaturated group such as trimethylolpropane triacrylate.

Description

Detailed Description of the Invention The present invention relates to a photosensitive composition for coating that is also suitable for paints and inks, and more specifically, a photosensitive resin that has excellent adhesion to metals and corrosion resistance, as well as good heat resistance and chemical resistance. The present invention relates to a composition.

Conventionally, solution-type and thermosetting types have been used as resist removers for various types of paints and inks, but in recent years, they have become more practical in terms of environmental pollution, workability, productivity, etc. Photo-curing type products have started to attract attention.

However, in general, photosensitive resin compositions tend to inhibit polymerization on metal surfaces due to the photopolymerization mechanism, making it difficult to obtain adhesion, and because they are rapidly cured, distortion occurs in the cured resin. Furthermore, since adhesion is inhibited, measures have been taken to improve adhesion, such as by roughening the metal surface by one-dimensional means, or by electrically or chemically treating it. In addition to increasing the number of processes, the expected effects may not be obtained, and if you try to balance adhesion, hardness, heat resistance, and chemical resistance, you will not be able to obtain the original performance of the cured resin. There are disadvantages such as not having

Especially when the photosensitive resin composition is used as a solder resist for printed circuit boards.

That balance can be particularly difficult.

The present inventors have overcome the drawbacks of such conventional photosensitive resin compositions, and have developed a composition that has excellent adhesion to metals and corrosion resistance,
As a result of intensive research to develop a photosensitive resin composition with good heat resistance and chemical resistance, we found that a certain amount of photopolymerization initiator, a prepolymer and monomer having certain ethylenically unsaturated groups, Add an unsaturated 7-ran compound, an unsaturated phosphoric acid ester, and further add a certain anti-repellent d-agent @ 7J
We have found that the first objective can be achieved by the following methods, and based on this knowledge, we have completed the present invention.

That is, the present invention provides (a) an epoxy (meth)acrylate type prepolymer or ester (meth)acrylate having ethylenically unsaturated groups at both ends; a photocuring component consisting of a prepolymer, a urethane acrylate type prepolymer, and a monomer having an ethylenically unsaturated group;
middle) 0.2 to 10% by weight based on the photocurable component; p) 0.1 to 3% by weight unsaturated silane compound based on the photocurable component; and 2) 0.2% by weight based on the photocurable component. 1 to 30 i amount of 2,4-diamino-6 based on ~5 weight molecule saturated phosphoric acid ester and (e) unsaturated phosphoric acid ester
- phenyl-1,3,5-1 riazine. B) The photocuring component of the coating material of the present invention includes an epoxy (meth)acrylate type prepolymer or an ester (meth)acrylate type prepolymer having ethylenically unsaturated groups at both ends, a urethane acrylate type prepolymer, and an ethylenic polymer. A combination with a monomer having a saturated group is used.The above urethane acrylate type prepolymer is a combination of an unsaturated aliphatic monocarboxylic acid ester having a hydroxyl group and a polyvalent isocyanate having a molecular weight of 500.
It is a reaction product having a general formula T (wherein R is a hydrogen atom or a methyl group, n is an integer of 1 to 4. A reaction product of acrylate or methacrylate having a hydroxyl group, such as a reaction product of a tetrabromobisphenol type A (or type F) epoxy compound and acrylic acid or methacrylic acid, and a polyvalent isocyanate. All of these can be obtained by reacting according to methods commonly used in the production of conventional urethane prepolymers.

In the coating material composition of the present invention, as the urethane acrylate type prepolymer in the photocurable component, particularly a partial ester of +Al tetramethylonylmethane and an unsaturated aliphatic monocarboxylic acid, for example, the above general formula (1) Excellent effects are exhibited when using a mixture of a urethane prepolymer derived from a polyvalent isocyanate and a urethane prepolymer derived from a polyvalent isocyanate. The above (A + acid component) does not need to be a single compound, but may be a mixture of compounds corresponding to the general formula (A) or a compound having two hydroxyl groups and at least one unsaturated group added thereto, and a polyhydric compound. It may also be a reaction product with iso7anate.

In the case of a mixture consisting of a compound represented by the above general formula (2), the composition is, in the general formula H, the component where n=1 is 5 mol or less, the component where n is 2 is 1 to 30 mol, and the component where n is 3. A component having a molar ratio of 20 to 60 and the remainder being n-4 is preferable.As the polyvalent isocyanate used for producing this urethane acrylate type prepolymer, tolylene diisocyanate, diphenylmethane-4,4'-
Diiso/anates are preferred. Addition of these urethane acrylate type prepolymers improves the chemical resistance and hardness of the cured film.

In the prepolymer used as (a) photocurable component of the present invention, when 1+1 of component (A) is 5% by weight based on the total amount of the prepolymer, the effect of addition is not significant, and 95% is %I'J , -Increased viscosity and high strain-
7-' is undesirable because it causes a decrease in adhesion.

A preferable range of fAl components is 15 to 40 parts by weight based on the total weight of the prepolymer.

In the present invention, epoxy (meth)acrylate refers to a reaction product of an epoxy compound of bisphenol A type (or F type) or novolak type polyhydric phenol and acrylic acid or methacrylic acid, bisoxyethylated bisphenol type A (or F diacrylate or dimethacrylate of type A (or type F), diacrylate or dimethacrylate of type A (or type F), tetrabromobisphenol
It is a reaction product of a W (! or F type) epoxy compound and acrylic acid or Q-L methacrylic acid, and ester (meth)acrylate is a reaction product of tetrahydroisophthalic acid and trimethylolpropane di(meth)acrylate. products, such as Aronix 8060 (Toagosei)
Co., Ltd.) etc.

Examples of the monomer having an ethylenically unsaturated group used in combination with the prepolymer in (a) photocuring component of the present invention include 2-hydroxyethyl acrylate, 3
-Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, tetraethylene glycol monoacrylate and their corresponding methacrylates, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate. -, ethylene glycol diacrylate, tetraethylene diglycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, pentaerythritol Examples include triacrylates, pentaerythritol tetraacrylates, and their corresponding methacrylates, which have a molecule iA° of less than 500.

These monomers (1'L) may be used alone, but it is preferable to use a mixture of two or more.Also, the ratio of prepolymer to these monomers is determined based on the market.
, it is preferable that the skin thickness is within the range of 0 to 6o15o. If the ratio of the prepolymer is less than 10/90, it is difficult to obtain the effect of using the prepolymer, and if it exceeds 60/15o, the adhesion will decrease and the viscosity of the composition will increase, causing the coating film 1
This results in a decrease in Te1. Prepolymers can significantly affect the rheological properties, curing speed, and physical properties of the cured film, whereas monomers have a diluting effect, but if the ratio of both is within the above range, the rheological properties will also be affected. Satisfactory membrane performance can also be obtained.

The photopolymerization initiator used as component (b) of the composition of the present invention (can be appropriately selected from those commonly used for photosensitive copper layers, but particularly preferred is c) pendyl. Dimethocinketanope is a mixture of 2-ethyl anthraquinone and l-chloroanthraquinone.The composition ratio thereof varies depending on the thickness of the cured film and other components used in combination, such as extender pigments and coloring pigments. usually,
Based on the weight of dimethoxy ketal, the amount of 2-ethylanthraquinone is 0.8 to 1.2 [r, 0.1 to 0.5 times the amount of 1-chloroanthraquinone, and the amount of 2-ethylanthraquinone and 1-chloroanthraquinone is Total a1 praise is 1
A range of 1.7 to 1.7 times the amount is preferable.

(b) The amount of added acid in the photopolymerization initiator must be 0.2 to 10% by weight based on (i) the photocuring component, and if the amount of addition is less than 0.2%, it is not practical. If the weight ratio exceeds 10, the performance deteriorates, and the cost is also high, which is disadvantageous.

The unsaturated silane compounds used as the (・→ component of the present invention) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, vinyltris(2-methoxyethoxy)7rane, 3- Examples include methacryloxypropyltrimethoxysilane.

These silane compounds may be used alone or in combination, and the amount added is 0.2% based on (a) photocuring component. 1~3jR-
It is necessary to select within the range of iJj'. By adding this unsaturated 7-run compound, the viscosity of the composition can be reduced and the effect of feeding can be obtained. The amount added is o
, the above effect was not observed in i-jukan-kami-X, and: 3%
Even if the amount exceeds 5%, no increase in effect by more than f% is observed.

In the present invention, the unsaturated phosphoric acid ester of component (2) is used as a metal-tightness improver, and leaves at least one phosphoric acid hydroxyl group in its molecule, and the others are vesicle-retaining. substituted esters, such as mono(2-methacryloquine/ethyl) phosphate, mono(2-acryloxethyl) phosphate, di(2-methacryloquinethyl) phosphate. , di(2-acryloxyethyl) phosphate, mono(2-methacrylogyethyl) [lljl)phosphate, and the like.

These unsaturated phosphoric acid esters may be used alone or in combination of one or two or more, and the amount added is as follows:
(a) It is necessary that the amount is in the range of 0.2 to 5% by weight based on the photocurable component. If the amount added is less than 0.2% by weight, no adhesion promoting effect will be observed, while if it exceeds 5% by weight, the curing properties will deteriorate.

In the composition of the present invention, component (e) 2,4-diamino-6-phenyl-1,3,5-)riazine is used as a corrosion inhibitor, and when combined with the unsaturated phosphoric acid ester, The prevention effect is further increased.

The amount added needs to be within the range of 1 to 30 parts by weight based on the unsaturated phosphoric acid ester of component (2). If the amount added is less than 1% by weight, the corrosion prevention effect will not be sufficient, and if it exceeds 30% by weight, no further effect can be expected, resulting in a cost disadvantage.

In addition to the above-mentioned ingredients, the photosensitive resin composition of the present invention may optionally contain various extender pigments, such as silica,
Merck, calcium oxide, lead oxide, alumina, titanium oxide, etc. can be added, and ultrafine powdered silica can be gradually added as a dispersion promoter, for example, 0.5 to 3%, depending on the application. It is also possible to add colored pigments or colored dyes.

The photosensitive coating material and composition of the present invention have excellent adhesion to metals and corrosion resistance, as well as good heat resistance and chemical resistance, and are particularly suitable for forming coating films on metal surfaces.

Next, the present invention will be explained in more detail with reference to Examples.

Reference Example 1 Manufacture of urethane acrylate dowel/polymer (+1) Bisphenol A type epoxy acrylate (Showa) Manufactured by Ryo Co., Ltd., trademark y, SP 150931so y
, tetramethylolmethane triacrylate [manufactured by Shin-Nakagi Kagaku Co., Ltd., trade name TMM-3] was collected in a round bottom flask containing 367Of$ and dibutyltin dilaurate 1.5S'Q5r, and heated in an oil bath at 70°C for 30 minutes. While stirring, heat the mixture to make a 1-to-2 solution. Next, add 64 (l) of tolylene diison anate to 30
After dropping for 1 minute, allow to react for an additional hour. After the reaction was completed, reaction 4 was determined to be 99.0% by titration. Also, trimethylolpropane triacrylate 50
The viscosity at 25° C. when made into a heavy eggplant solution was 35 voids using a BH type viscometer.

Reference Example 2 Urethane acrylate prepolymer (manufactured by Bisphenol A type epoxy acrylate manufactured by Showa Kobunshi Co., Ltd., trade name SP 1506 X) 465 t
The reaction was carried out in the same manner as in Reference Example 1, except that . The reaction rate determined by the titration method was 99.2%, and the viscosity at 25° C. of a 50-h1 solution of trimethylolpropane triacrylate was 4 $ 3 voids using a BI (type viscometer).

Example 1 Bisphenol A type epoxy acrylate (SP 1509) 5009, urethane acrylate prepolymer (I) 2007 obtained in Reference Example 1, trimethylpropane triacrylate (TMPTA) (T
MPTA) 982f, 2-hydroxyethyl methacrylate (211FMA): 3 (38?) Dimethoxyketal (manufactured by Ciba Geigy, trade name Irgacure (i51)) 24F, 1-chloroanthraquinone 1O2,2 as a photopolymerization initiator - Add ethyl anthraquinone 21 and then mono(2-methacryloxyethyl) phosphate.
162.2,4-diamino-6-phenyl-L3,5-
Triazine 1.62.3-methacryloxypropyltrimethoxysilane 142, Phthalocyanine Green 302 as a coloring pigment, and 1200 g of talc as an extender pigment were added and kneaded with a five-roll mill. The viscosity of the composition is BH type viscosity a1, which is +40 voices at 25°C.

The composition thus obtained was coated on copper foil with a bar coater to a thickness of 15 pm, and was heated at 120 W/rm
Full exposure with 3 metal halide lamps (12tyn/+71cm) at a conveyor speed of 6 full/min
I! turned into

The results are shown in section 1k along with the composition of each component.

Comparative Examples 1 to 6 A composition was prepared in exactly the same manner as in Example 1, except that the composition of each component in +ll was changed as shown in Table 1. The results are shown in Table 1.

/ \ \ /\111, /''/' / 1Ll) 3-methacryloxypropyltrimethoxysilane 2) Mono(2-methacryloxyethyl) phosphate 3)
2.4-diamino-6-phenyl-1,3,5-triazine Example 2, Comparative Example 7 Novolak-type epoxy acrylate [Showen Kobunshi Co., Ltd.
Co., Ltd., trade name SP 4010) 1000 y, in Reference Example 1 (also urethane acrylate prepolymer (112
00y (50% TMPTA solution), trimethylolpropane triacrylate 442F, 2-hydroxymethacrylate-1368F, and benzyl dimethoxyketal (the above-mentioned Irgacure (i51)) as a photopolymerization initiator.
24r,l-chloroanthraquinone 92.2-ethylanthraquinone 191 was added, and further mono(2-methacryloxyethyl) phosphate 211.2.4-diamino-6-
Phenyl-1,3.5-triazine 1.6F, 3-methacryloxypropyl trimethochine/Ran 142, Phthalocyanine Green 302 and Aerosil 452 as coloring pigments, and 120 of talc as extender pigment were added and kneaded with three rolls. The viscosity of the composition is 1 using a BH type viscometer.
The composition obtained in this way was coated with a bar coater for 15 minutes at a temperature of 60 voids/25°C.
Coated to a thickness of μm [7,120W/LynX 3 lights (1
6 t using 2(-In height) metal halide lamp
It was exposed and cured at a conveyor speed of i/min. The results are shown in Table 2.

For comparison, a composition was prepared in the same manner as in Example 2, coated on a copper foil, and exposed. (Comparative Example 7).

The results are shown in Table 2.

Table 2 Example 3, Comparative Example 8 Instead of SP4010, a reaction product of tetrahydroisophthalic acid and trimethylolpropane acrylate was used (manufactured by Tobu Gosei Co., Ltd., trade name: Aronix 81HiOJ). In the same manner as in Example 2, a composition was prepared in step 2, applied to copper foil 1, and cured by exposure. The results are shown in Figure 3.

The urethane acrylate prepolymer (without using 11, the above prepolymer 1400
A composition was prepared in exactly the same manner as in Example 3, except that only f was used [7], and the composition was coated on copper foil and cured by exposure. The results are shown in Table 3.

Table 3 Agent Akira Agata

Claims (1)

[Claims] 1 (a) Evogish (meth)acrylate type prepolymer or ester having ethylenically unsaturated groups at both ends (
A photocuring component consisting of a meth)acrylate type prepolymer, a urethane acrylate type prepolymer, and a monomer having ethylenic vesicle activity, (rJ) 0.2 to 10% light based on the facilitation component. Polymerization initiator, (based on photo-curing component (), 1-3-layer unsaturated silane compound, photo-curing) K-based 0.2-5 layer vesicles: fu 2,4-diaminohe6-phenyl-1,3.5-) liazine based on 1 to 30 t-dimers based on 1:J9 unsaturated phosphoric acid ester and 2,4-diaminohe6-phenyl-1,3. Photosensitive IIt, +co, -ching material,
.