JPS58187414A - Photosetting composition - Google Patents

Abstract

PURPOSE:The titled composition that comprises an unsaturated acrylic oligomer, an acrylic or methacrylic ester of a specific alcohol, a polyfunctional acrylic or methacrylic ester and a photosensitizer, thus giving a cured product with high water, solvent and heat resistance. CONSTITUTION:The objective composition comprises (A) 100pts.wt. of an unsaturated acrylic or methacrylic oligomer having 200-3,000 molecular weight and 2 or more acryloyl or methacryloyl groups in one molecule, such as epoxy acrylate (B) 0.5-50pts.wt. of an acrylic or methacrylic ester of an alcohol having a fluorinated alkyl and/or alkylene group, (C) 0-80pts.wt. of a polyfunctional acrylic or methacrylic ester such as trimethylolpropane triacrylate and (D) 0.1-10pts.wt. of a photosensitizer.

Description

Detailed Description of the Invention The present invention provides cured films and other cured molded products that are cured by light and have excellent water resistance, solvent resistance, heat resistance, stain resistance, slipperiness, water repellency, and oil repellency. The present invention relates to photocurable compositions that can be produced, and mainly relates to photocurable compositions useful for producing paints, adhesives, and cast products.

The main reasons why photocurable compositions have traditionally been used for manufacturing paints, adhesives, and cast products are (a) high curing speed, which improves productivity; and (b) curing performance. , no solvents or water are generated, and the work environment is excellent.

(c) Since it can be handled at room temperature, it is advantageous when used as a paint, for example, when applied to heat-unstable substrates;
Additionally, there is no risk of the monomer decomposing under heat and turning into a non-hardening compound, and (2) there is little curing shrinkage.

A variety of photocurable compositions have been developed and used, but the cured products have excellent properties such as stain resistance, water repellency, oil repellency, weather resistance, slipperiness, and mechanical strength. It's not satisfying.

For example, a photocurable composition has been proposed that uses epoxyacrylate, which is a reaction product of engineered resin and (meth)acrylic acid, as a photocurable base polymer and blends a photosensitizer with it. has been done. However, the cured product obtained from this photocurable composition has relatively good adhesion and hardness.
However, it has drawbacks such as inferior surface weatherability, water repellency, oil repellency, and stain resistance, and has not yet shown sufficiently satisfactory effects.

The performance required of a photocurable composition varies depending on the application and cannot be determined unconditionally, but in general, (I) rapid curing, (2) excellent workability, and Qll) curing. The properties of the material, such as hardness, heat resistance, cold resistance, electrical properties, and adhesion, are suitable for the application field; (IV) The cured product has excellent light resistance and weather resistance, and is resistant to yellowing and aging. ■) When the cured product is exposed outdoors, it is difficult to get dirty; (B) When the cured product is exposed to water or solvent, it is water and oil repellent and does not get wet easily. However, a photocurable composition that simultaneously possesses all of the above desirable properties has not yet been found.

As a result of various studies regarding photocurable compositions that satisfy the above performance, the present inventors discovered that a photocurable composition containing a specific fluorinated alkyl group and/or alkylene group-containing acrylic ester or methacrylic ester of an alcohol. The present invention was completed by discovering that a curable composition can fully satisfy the above requirements.

That is, the present invention provides (13) fluorination for 100 parts by weight of an unsaturated acrylic oligomer having a molecular weight of 200 to 3,000 and having at least two acryloyl groups or methacryloyl groups in one molecule. 0.5 to 50 parts by weight of acrylic ester or methacrylic ester of alcohol having an alkyl group and/or alkylene group ((8
) A photocurable composition containing θ to 80 parts of a polyfunctional acrylic acid or methacrylic ester, and (I) 01 to 10 parts of a photosensitizer.

The (t)acrylic oligomers used in the present invention include the following types.

(1) An unsaturated spiroacetal oligomer having a spiran structure in the molecule and at least two unsaturated bonds. It is a reaction product with a compound having one acryloyl or methacryloyl group.

(2) EBOKI 7 acrylate oligomer It is a reaction product of an epoxy resin having at least two epoxy groups in one molecule and acrylic acid or methacrylic acid, and the epoxy resins include bisphenol-diglyndyl ether type, novolac-polyglyceride, :) Examples include ether type, glycidyl ester type, and peracetic acid type.

(3) Urethane acrylate oligomer Various types of this oligomer are known, but in general, unsaturated alcohols having an acryloyl group and a hydroxyl group in the same molecule, polyols, polyethers, or hydroxy polyesters are used. It is obtained by reacting with diisocyanate, with or without using it together.

(4) Polyester acrylate oligomers synthesized by the reaction of an unsaturated evoquin compound such as glycidyl acrylate or methacrylate with a polybasic acid anhydride, or a condensation product of a polyhydric alcohol, polybasic Vl & or its acid anhydride. It is synthesized by esterification with acid or methacrylic acid.

(5) Polyether acrylate oligomer Synthesized by esterifying the terminal hydroxyl group of a polymer or copolymer of a polyhydric alcohol such as ethylene glycol, propylene glycol, butylene glycol, or glycerin with acrylic acid or methacrylic acid.

The unsaturated acrylic oligomer (A) has a molecular weight of 200 to 3,000 and has at least two 7-acryloyl groups or methacryloyl groups in one molecule. If the molecular weight of component (A) is less than 200, film-forming properties will be insufficient when used as a paint or adhesive;
When used in the production of cast products, it has drawbacks such as brittleness and low impact resistance. On the other hand, if the molecular weight exceeds a or ooo, the viscosity will become too high and when used as a paint or adhesive, not only will the paintability deteriorate, but also the adhesion to the substrate will not improve, which is undesirable. . Furthermore, when used in the production of cast products, it has drawbacks such as low hardness, low heat distortion, and low oil resistance.

Component (A) may be used singly or in combination of 28 or more. These (N components) have excellent photocurability, and their cured products have excellent toughness, water resistance, and solvent resistance.
(By selecting the wires of the N component, a desired cured product ranging from a soft cured product to a hard cured product can be formed.

(B) 7-nominated alkyl group and/or
Alternatively, an acrylic ester or methacrylic ester of an alcohol having an alkylev group is one in which some or all of the hydrogen atoms of the alkyl group or alkylene group are substituted with a Fluorine chain, and the carbon atoms of the alkyl group, alkylene group, or these inner groups in one molecule are Acrylic esters or methacrylic esters of alcohols having a total number of 1 to 30, examples of which include the following compounds.

111i'20-(OF2)n-(OH2)m-000
−0=OH2■ (jF3−(OF2) .−(CI(,,)m−000
-0=OH2■ ORX R'
= +1 or II, to (1, \-■ or C1
1,, ro'=11 or tau, (for +).

and (b) hooks of + et al., alkyl groups and /i or alkylev groups: 1-9 acrylic acid esters or r [methacrylic esters are photocurable The cured product formed from the 01 composition obtained by blending this with 1'l has stain resistance, water repellency, oil repellency, and anti-aging properties.
It has excellent resilience.

() 3) Component formulation 1 (the amount is χ·1 in the (A) acrylic oligomer 100 mold breakage part, 05 to 50 parts, preferably 1 to 30 parts) (I4 ) If the blended amount of the component is small, it is not preferable because the water repellency, oil repellency, stain resistance, slipperiness, etc. are insufficient.

(13) If too much of the component is added, not only the adhesion to the substrate will deteriorate, but also the photocuring speed will decrease, which is not preferable.

In the present invention, if necessary, (0) polyfunctional acrylic ester or methacrylic ester (N acrylic oligomer and (B)
J
(t can be used together. Here ((J '4
IT C1 The acrylic ester or methacrylic ester has at least 211^1.
(2 to 4 acryloyl or methacryloyl groups are copolymerized with (N component or (13) component)
1' If: Any material may be used as long as it can be mixed uniformly. Examples of these are ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate.

Probylene glycol diacrylate, polypropylene glycol diacrylate, butylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, diglyphyl bisphenol A diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, diglyphyl bisphenol A dimethacrylate, and the like. .

These (Q components) have excellent photopolymerizability, and by blending them, the viscosity of the composition is reduced, workability is improved, and the hardness of the cured product formed from the composition is increased.

In the present invention, component (C) which is optionally blended into the photocurable composition is (A) acrylic oligomer 10
For 0 parts by weight, θ ~ 80 parts by weight, 0 to 5 parts by weight
It is 0 parts by weight. (If the amount of component (3) is too large, the cured product will not only become hard and brittle, but also have insufficient adhesion to the base material when used as a paint or adhesive, and will harden due to wear.) It has the disadvantage that objects tend to fall off.Furthermore, in the case of cast products, if the amount of component (0) is too large, the cured product becomes brittle and has a disadvantage of reduced impact strength.

As the photosensitizer used in the photocurable composition of the present invention,
Any known photosensitizer may be used; for example, benzyl, pencil/pencil/methyl ether, benzoin isopropyl ether (thioxanthone, methyl orthobenzyl benzoate, azobisisobutyronitrile, etc.) may be used. can.

The blending amount of the photosensitizer is (A) acrylic oligomer 10
The amount is 0.1 to 10 parts by weight relative to 0 parts by weight.

If the amount of photosensitizer is too small, curing takes a long time, which is undesirable, and if the amount of photosensitizer is too large, it is not only economically undesirable, but also has a particularly noticeable effect on curability. No effect was observed.

The photocurable composition of the present invention may contain surfactants, leveling agents, antifoaming agents, diluents, coupling agents, Dyes, pigments, refractory agents, and other additives can be added.

The photocurable composition of the present invention can be cured by light to produce cured films and other cured molded products with excellent water resistance, solvent resistance, heat resistance, stain resistance, slipperiness, water repellency, oil repellency, etc. Because of its properties, it is useful for manufacturing coatings, paints, adhesives, linings, laminates, and cast products for metals, textiles, leather, paper, plastics, etc.

As a method for photocuring the photocurable composition of the present invention, a xenon lamp, an arc lamp, a low pressure or high pressure mercury lamp is used. Since the photocurable composition of the present invention can be sufficiently cured even in the presence of air, it does not particularly require an inert gas as an atmosphere.

In order to produce a cast product using the photocurable composition of the present invention, after filling the composition into a mold of any shape made of a material transparent to light, In order to form a cured film on a substrate using the photocurable composition of M, the substrate is coated with the composition using a roller, spray, brush, etc., or the substrate is impregnated with the composition and then coated with the composition using a roller, spray, brush, etc. The method used is to squeeze the adhesive to a predetermined amount and then irradiate it with ultraviolet rays to cure it.

Hereinafter, misfire 8A' will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 Based on 100 parts by weight of 484 epoxy acrylate obtained by reacting 1 mole of a combination of bisphenol A and epichlorohydrin (11 chs per epoxy) and 2 moles of acrylic acid in the presence of a basic catalyst A photocurable composition was prepared by blending 50 parts by weight of trimethylolpropane triacrylate, 1 part by weight of 5 parts of hydrogenated alkyl acrylate expressed by the following formula % (2), and 21 parts of benzoin propyl ether. .

This photocurable composition was placed in a silicon-lined glass mold, and then cured by irradiating 2-fraction ultraviolet light from a distance of 3ocrn using a 200 W/in high-pressure mercury lamp to form a plate with a thickness of 5WrM. Created a molded product.

The performance of this plate-shaped molded product (measured according to RRS K 6911) is shown in Table 1.

Comparative Example 1 A plate-shaped molded product was produced in the same manner as in Example 1, except that a photocurable composition without fluorinated alkyl acrylate B was used. The performance of this plate-shaped molded product is shown in Table 1.

Table 1 As is clear from Table 1, the mechanical properties of molded articles made from the photocurable composition of the present invention are different from those after molding at 1,000 m
There is almost no red after 0 hour weather meter exposure,
There is also no dirt on the surface. In addition, the mechanical strength of molded products made from photocurable compositions that omit fluorinated alkyl acrylates shows a large difference between after molding and after exposure to a weatherometer for 1,000 hours. It was also very dirty.

Example 2 0 as a terminal group from ethylene glycol and adipic acid
An oligomer having an average molecular weight of 1080 was prepared, and both terminal OH thereof were acrylated to produce polyester acrylate.

A photocurable composition having the following blending ratio was prepared using this polyester acrylate as a base.

Polyester acrylate 100 parts by weight* Fluorinated alkyl acrylate 30 71 Titanium white (rutile) 50 l Benzyl
21*OF, -(OF' 2 )
5-8o 2-NH-OH2-Cl0O-OH=OH
,.

This composition was applied to a galvanized steel plate coated with an epoxy primer.
After coating to a thickness of 0 microns, it was cured by passing a 300 W high pressure mercury lamp through a distance of 1 ocrn for 2 seconds.

The performance of the cured film (measured according to JIS K 5400) and the performance of the cured film after applying it to a weatherometer for 1,000 hours are shown in Table 2, and almost no deterioration was observed. .

Table 2 Comparative Example 2 A photocurable composition obtained by removing the fluorinated alkyl acrylate from the formulation of Example 2 was used in the same manner as in Example 2 to +If! , coated on a lead steel plate and hardened by ultraviolet light.

The performance of the cured film and the performance of the saponified film after i, ooo hours and weather meters are evaluated according to JIS K.
Table 3 shows the results measured in accordance with 5400.

As is clear from Table 3, the performance of the cured film was very similar to that of Run 2, but the weatherometer showed no i,oo.
After o hours, the cured film deteriorated significantly. In addition, the appearance of the test piece after being exposed to the Weatherometer for 1,000 hours was almost the same as that after curing in Example 2, and had excellent water repellency, but in Comparative Example 2, no chalking was observed. I fell asleep.

Table 3 Patent applicant: Showa Denko Co., Ltd. Showa Kobunshi Co., Ltd. Representative Patent Attorney Sei Kikuchi

Claims (1)

[Scope of Claims] (~ Based on 100 parts by weight of an unsaturated acrylic oligomer having a molecular weight of 200 to 3,000 and having at least two acryloyl groups or methacryloyl groups in one molecule, (B) fluorinated 05 to 50 parts by weight of an acrylic ester or methacrylic ester of an alcohol having an alkyl group and/or an alkylene group.