JPS6341520A - Polyurethane (meth)acrylate resin composition - Google Patents

Abstract

PURPOSE:To obtain titled composition, by blending a polyurethane (meth)acrylate resin with isocyanuric acid, etc., in a specific proportion, readily curable by irradiation with active energy rays or heating in a short time and capable of imparting improved heat resistance for films. CONSTITUTION:A composition consisting of (A) 100pts.wt. reaction product of (i) 100pts.wt. di- or triisocyanate of an isocyanuric acid derivative, carbodiimide-modified diphenylmethane diisocyanate or polyisocyanate having diphenylmethane with (ii) 10-250pts.wt. low-molecular weight compound containing at least >=2 active hydrogen atoms in one molecule, acid anhydride or bi- or polyfunctional glycidyl compound and (iii) 55-200pts.wt. acrylic acid derivative and (B) 3-40pts.wt. (meth)acrylate of isocyanuric and a derivative thereof, di- or triallyl isocyanurate or di(meth)acrylate having bisphenol S.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyurethane (meth)acrylate resin composition, and more specifically, the present invention relates to a polyurethane (meth)acrylate resin composition that can be easily cured by irradiation with active energy rays and/or heating for a very short time. The present invention relates to a polyurethane (meth)acrylate resin composition that is useful as a constituent material of a film that has particularly excellent heat resistance.

[Prior Art] Conventionally, various heat-curable resin compositions or active energy ray-curable resin compositions such as ultraviolet rays or electron beams have been used for coating various base materials such as plastics and metals due to their easy curability. ing.

As such resin compositions, for example, those containing polyurethane resin as a main component are known. For example, JP-A-59
Publication No. 8714 describes polyurethanes such as hydroxyl-terminated polyesters, polyethers, or
An electron beam curable polyurethane resin composition containing a reaction product of an unsaturated polyether with a specific degree of unsaturation and an organic diisocyanate is disclosed, and also disclosed in JP-A-59-5641.
No. 8 discloses an electron beam curable polyurethane resin composition in which the reaction product in the above publication further contains an acrylate or alkalkylate-terminated polyurethane. All of the resin compositions are excellent in that they can be easily cured by irradiation with electron beams, and the cured products thereof are also excellent in terms of tensile strength, elongation rate, and the like. However, these polyurethane resin compositions are used as binder resins for magnetic tapes, and as a matter of course, physical properties such as tear strength are not particularly required for their cured products.

Furthermore, JP-A-60-90211 discloses (a) organic di- and/or I-liisocyanates, (b) di- and/or trihydroxy polyethers, (c) divalent or trivalent
It is a reaction product of an organic alcohol compound and/or two organic amine compounds, and (d) an acrylate compound having at least one group selected from 1M hydroxyl group and carboxyl group in one molecule, and a certain number of acrylate compounds. An ionizing radiation-curable urethane resin composition containing as a main component a reaction product having a specific repeating unit of item-1- is disclosed, and JP-A-60-90212 discloses (a) organic di- and / or triisocyanate, (b) di and/or trihydroxy polyether, and (c) free hydroxyl group,
A reaction product of an acrylate compound having at least one group selected from carboxyl groups in one molecule,
An ionizing radiation-curable urethane resin composition containing a reaction product having a certain number or more of specific repeating units as a main component is disclosed. All of these urethane resin compositions can be treated by irradiation with an electron beam or the like, similar to the above-mentioned compositions.
It is made of urethane that hardens easily. However, these compositions are used as coatings on the outer surfaces of leather, furniture, etc. for the purpose of imparting functions such as moisture permeability, antifogging, and sweat prevention.

As described in detail below, conventionally known polyurethane resin compositions are used as binders for magnetic tapes and as coating agents for various substrates, but they have not yet been made into films for various uses. Not done.

[Problems to be Solved by the Invention] The present invention aims to cure conventional polyurethane compositions that have not been put to practical use as films by irradiating them with active energy rays such as ultraviolet rays or electron beams or by heating them. The object of the present invention is to provide a polyurethane resin composition that can be used as a constituent material of a film, and the obtained film has excellent various physical properties, especially heat resistance.

[Means and effects for solving the problems] The polyurethane (meth)acrylate resin composition of the present invention comprises (A) (a) di- or triisocyanate of an isocyanuric acid derivative, carbodiimide-modified diphenylmethane diisocyanate, diphenylmethane diisocyanate, and diphenylmethane. At least one member selected from the group consisting of polyisocyanates having the structure, 100 double star parts; (b) a low molecular weight compound containing at least 2 inverted -1- active hydrogens in one molecule, an acid anhydride, and a difunctional 10 to 250 parts by weight of at least one selected from the group consisting of the above glycidyl compounds; and (c) (meth)acrylic acid derivatives having a functional group capable of reacting with (meth)acrylic acid or isocyanate (. group); 55 to 200 parts by weight; 100 parts by weight of the reaction product; and (B) (meth) of isocyanuric acid or a derivative thereof.
3 to 40 parts by weight of acrylate, di- or triallyl isocyanurate, or di(meth)acrylate having a bisphenol S-type structure;

The polyurethane (A) component constituting the composition of the present invention (
The meth)acrylate resin can be produced using the following components (a), (b), and (c) as starting materials.

Component (a), which is a raw material for producing component (A), is at least one member selected from the group consisting of di- or triisocyanates of isocyanuric acid derivatives, diphenylmethane diisocyanate modified with carbodiimide, diphenylmethane diisocyanate, and polyisocyanates having a diphenylmethane structure. It is. Therefore, two or more of these compounds can be used in combination as component (a). Examples of the di- or triisocyanate of the isocyanuric acid derivative which is the component (a) include (cH2)6NCO (cH2) s NCO (cH2) a NCO; and diphenylmethane diisocyanate modified with carbodiimide. Examples of the polyisocyanate having a diphenylmethane structure include: Millionate MT
, Millionate MTL and Millionate MR (product name;
(manufactured by Nippon Polyurethane Industries).

Component (b) is at least one selected from the group consisting of low molecular weight compounds containing at least two or more active hydrogens in one molecule, acid anhydrides, and difunctional or more-1-glycidyl compounds. Therefore, each of these compounds is
2) can be used in combination with component (b).

Among the components (b), examples of compounds containing at least two or more active hydrogens in one molecule include methylene glycol, ethylene glycol, 1,4-butanediol, 1,3-butanediol, 2.3-butanediol, etc. - Dihydric alcohols such as butanediol, 1,5-menthanediol, ■, 8-octanediol and 1,10-decanediol; succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, cepatine acid, phthalic acid,
Divalent carboxylic acids such as maleic acid and itaconic acid; and 1,2-ethylenediamine, 1,2-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, Examples include divalent amines; further examples include polyols, polycarboxylic acids, and polyamines having three or more active hydrogen atoms in one molecule. Examples of the acid anhydride include succinic anhydride, maleic anhydride, trimellitic anhydride, Himic anhydride, pyromellitic anhydride, and phthalic anhydride. In addition, examples of glycidyl compounds having more than two functionalities include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, i-limethylolpropane polyglycidyl ether, and the like. be able to.

Component (c) is a methacrylic acid or acrylic acid derivative having a functional group that can react with methacrylic acid or acrylic acid or an isocyanate group. In the component (c), examples of the methacrylic acid or acrylic acid derivative having a functional group capable of reacting with an incyanate group include glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, Examples include (meth)acrylamide and N-methylol (meth)acrylamide. Two or more of these compounds of component (iii) can also be used in combination.

Component (A) is manufactured using components (a) to (c) listed in "-" as raw materials, and the manufacturing method thereof is, for example, as follows.

Each component (a) to (c) is dissolved in an inert solvent such as toluene, xylene, ethyl acetate, cyclohexanone, etc.
Dissolve it to a concentration of about 1.2 to 1.6 g/-,
Then, the reaction is carried out at about 60 to 80°C for about 5 to 10 hours.

After the reaction is completed, the inert solvent is removed while heating under reduced pressure to obtain the polyurethane (meth)acrylate resin of component (A). The amount of components (a) to (c) used in the production of component (A) is 10 to 250 parts by weight, preferably 5 to 150 parts by weight of component (b) per 100 parts by weight of component (a). Parts by weight, component (c) is 55 to 20
0 parts by weight, preferably 80 to 150 parts by weight. Furthermore, when producing component (A), a polymerization initiator such as di-n-butyltin dilaurate or a polymerization terminator such as methanol may be used as necessary.

Component (B) constituting component (B) of the present invention is a group consisting of methacrylate-1 or acrylate of isocyanuric acid or its derivative, di- or triallyl isocyanurate, and dimethacrylate or acrylate having a bisphenol S type structure. at least one selected from
It is a seed. Therefore, two or more such compounds can also be used in combination. In the component (B), examples of methacrylates or acrylates of isocyanuric acid or its derivatives include CH2CH2C00CH=CH2 CH2CH20CO(cH2) s 0COCH=C, and examples of di- or triallyl isocyanurate include, (2) Examples of the dimethacrylate or acrylate having a bisphenol S type structure include H3 H and the like.

The composition of the present invention is composed of components (A) and (B) described in -1-, and the blending ratio in the composition is (A).
Component (B) is used in an amount of 3 to 40 parts by weight, preferably 5 to 30 parts by weight, relative to 100 parts by weight of component (B). If the blending ratio of component (B) is less than 3 parts by weight, it will hardly contribute to heat resistance, and therefore a heat-resistant film may not be obtained, and if it exceeds 30 parts by weight, the rigidity of the cured product will be too strong. When made into a film, it lacks bendability and cannot be put to practical use as a film.

Furthermore, when curing the composition of the present invention and using ultraviolet rays as active energy rays, a photosensitizer is added. Examples of the photosensitizer include aromatic hydrocarbons,
Examples include benzophenone and its derivatives, 0-benzoylbenzoic acid ester, acetophenone and its derivatives, benzoin, benzoin ether and its derivatives, quinone compounds, and amines. Among such photosensitizers, aromatic hydrocarbons include, for example, phenanthracene, chrysene, anthracene, etc.; benzophenone and its derivatives include, for example,
Benzophenone, 2,4-dimethylbenzophenone, 2
, 4-dichlorobenzophenone, and 4,4'-bisbenzophenone; examples of 0-benzoylbenzoate include 0-benzoylbenzoate, 0-benzoylbenzoate methyl ester, and o-benzoylbenzoate. Examples include benzoylbenzoic acid ethyl ester and 0-benzoylbenzoic acid phenyl ester; examples of acetophenone and its derivatives include:
Examples of benzoin, benzoin ether and derivatives thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Examples of quinone compounds include n-butyl ether and benzointriphenyl ether; examples of quinone compounds include benzoquinone, naphthoquinone, anthraquinone and 5.12
Examples of the amines include diphenylamine, carbazole and triphenylamine; one or more of these photosensitizers can be used.

The blending ratio of the photosensitizer is 1 to 7 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of component (A). If the proportion of the photosensitizer is less than 1 part by weight, curing will be insufficient, and even if it exceeds 7 parts by weight, it is no longer possible to improve the curing speed by 1■, and on the contrary, the manufacturing cost will increase. It is undesirable because it invites. In addition, the above (A
) and (B), a heat-curable composition can be obtained by further incorporating a heat sensitizer.

Examples of the heat sensitizer include inorganic peroxides, organic peroxides, and azo compounds. Among such heat sensitizers, examples of inorganic peroxides include potassium persulfate and ammonium persulfate; examples of organic peroxides include benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and acetyl peroxide. Examples of azo compounds include azobisisobutyronitrile, azobispropionitrile, diazo Examples include aminobenzene and p-nitrobenzene diazonium salt; one or more of these can be used. The blending ratio of such a heat sensitizer is 0.1 to 1 part by weight per 100 parts by weight of component (A);
Preferably it is 0.2 to 0.7 parts by weight. When the blending ratio of the heat sensitizer is outside the above range, it is not preferred for the same reason as when a photosensitizer is blended. Furthermore, the composition of the present invention can contain both such a photosensitizer and a heat sensitizer.

The composition of the present invention consists of the above-mentioned components (A) and (B), and a sensitizer if necessary. Fillers, antistatic agents, magnetic powders, fragrances, antibacterial agents, enzymes,
Flame retardants, glass peas, plastic powder, wood flour, etc. can be blended.

The composition of the present invention thus obtained is useful as a constituent material for a film, and the film can be produced, for example, by the following method.

First, the composition of the present invention is heated to make it liquid.

Next, the liquid material is applied to a suitable substrate such as a polyethylene terephthalate resin film using an applicator or the like so as to have a uniform thickness. Thereafter, the coated material can be cured by irradiation with active energy rays or heating to obtain a film.

In the method for manufacturing such a film, the thickness after coating 4i can be appropriately determined depending on the use of the film. In addition, when curing by irradiation with active energy rays,
For example, electron beams, X-rays, α-rays, β-rays, γ-rays, ultraviolet rays, etc. can be used. Irradiation conditions vary depending on the type of active energy ray used, film thickness, and film composition, but for example, when using an electron beam, the irradiation intensity is about 1 to 20 Mrad. Irradiation intensity is IM
If rad vortex is not used, curing will generally be insufficient and the resulting film will remain sticky.

Even when it exceeds 20 Mrad, there is almost no difference in the curability or the physical properties of the resulting film.

Also, for example, when using ultraviolet light, usually l
Under the condition that the object to be irradiated is placed at a distance of 15 cm vertically below the KW (80 W/cm) high-pressure mercury lamp,
An irradiation time of several seconds is sufficient. When curing by heating, heating at a temperature of 100° C. or higher for about 10 minutes is usually sufficient. Further, when manufacturing a film, curing by irradiation with active energy rays and curing by heating can be combined. for example,
First, it can be precured with an electron beam or ultraviolet rays, and then it can be completely cured by heating, or it can be cured in the reverse order of operations. Such a curing method can be appropriately selected depending on the workability and the physical properties of the film to be obtained.

Films containing the composition of the present invention obtained in this way are, for example, flexible printed wiring films, various heat-resistant tape substrates, infrared absorbing films, ultraviolet absorbing films, antibacterial films, [films, peelable It can be applied to films, liquid crystal encapsulation films, etc.

[Examples of the invention] Example 1 (cH2) s NCO 〇Toluene 800g di-n-butyltin dilaurate 1g 1.6-hexanediol 472g methacrylic acid-2-hydroxy
1040g ether methanol 300g above triisocyanate compound toluene and dilauric acid di-n
- Butyltin is placed in a 5-liter reaction vessel equipped with a thermometer, a +V stirrer, a cooling tube, a nitrogen gas inlet tube, and a dropper, and then heated to 60°C while stirring, A liquid product was obtained. Then, while maintaining the liquid temperature at 60°C,
1.6-hexanediol was added dropwise once every 4 hours. Next, 2-hydroxyethyl methacrylate was added dropwise over about 1 hour while maintaining the liquid temperature at 80°C or below, and after the dropwise addition was completed, the liquid temperature was maintained at 70°C for about 3 hours. After that, methanol was added, and after stirring for about 1 hour, the solvent was removed while heating under reduced pressure to obtain 5,700 g of a 100% solid polyurethane methacrylate resin having the following formula and a molecular weight of 1452. Obtained.

Using the resin thus obtained, a polyurethane methacrylate-1 resin composition having the following composition was obtained.

Films were made using such compositions. first,
This composition was heated at 60-70°C to obtain a low viscosity liquid. Next, this liquid material was applied onto the polyethylene terephthalate resin film 7 using an applicator so as to have a uniform thickness. After that, under a high-pressure mercury lamp of IKW (80 W/cm) in a nitrogen stream, 15C
Irradiate ultraviolet rays for about 2 seconds from a distance of I11 to a thickness of 10
A 0- film was obtained.

Example 2 (-NCO group content 30% Luene 400g di-n-butyltin dilaurate 1g cepacic acid
808g methanol
Using 30g-1 of each component, in the same manner as in Example 1, 1, which is represented by the following formula and has a molecular weight of 930, was prepared in the same manner as in Example 1.
00% solids polyurethane methacrylate resin 37
00g was obtained.

Using CH2CH20COCH=CH2 or the resin thus obtained, a resin composition having the following composition was obtained.

Polyurethane methacrylate 100 g Resin diacetone acrylamide 100 g Aronix M-315 100 g Using such a composition, instead of UV light, intensity 3 M
A light bamboo-colored film with a thickness of 75 mm was prepared in the same manner as in Example 1 except that it was cured with a rad electron beam.

Example 3 Toluene to00g di-n-butyltin dilaurate 1g hexamethylene diamine 464g methanol
32g1- Using each component listed below, in the same manner as in Example 1, 100
% solids of polyurethane acrylate resin was obtained.

Using the resin thus obtained, a resin Ml composition having the following composition was obtained.

Irgacure 651 9g (trade name; manufactured by IC1) Using this composition, a thickness of 75% was prepared in the same manner as in Example 1.
I got a film of Le.

Example 4 Toluene 700g di-n-butyltin dilaurate 1g 1,4-butanediol 360g methacrylic acid
688g methanol 32
A polyurethane methacrylate resin having a solid content of 100% and having an average molecular weight of 950 and having an average molecular weight of 950 was obtained in the same manner as in Example 1 using each of the components listed in "g" 2.

Using the resin thus obtained, a resin composition having the following composition was obtained.

Using such a composition, a thickness of 14 was obtained in the same manner as in Example 1.
A 0μ film was obtained.

Example 5 A resin composition having the following composition was obtained.

Resin composition obtained in Example 2 A film with a thickness of 70p was obtained in the same manner as in Example 2 using 100 g of the composition.

Example 6 A resin composition having the following composition was produced.

A film was obtained in the same manner as in Example 1, except that 100 g of the resin composition obtained in Example 2 was used and the composition was cured by heating at 130° C. for 20 minutes.

The following tests were conducted on each of the films of Examples 1 to 6 obtained as described above-1-. Also, the thickness is 340
A similar test was conducted on the polyethylene terephthalate film of g, and this was used as a comparative example. The results are shown in Table 1.

Tensile strength: Strength at break 1 was measured using an Instron type tensile tester at a tensile speed of 300 mm/min.

Elongation rate: using an Instron type tensile tester, tensile speed 3
The elongation at break was measured at 00 mm/min.

Tear strength was measured according to ASTM D1004-61.

Heat resistance: Immersed in a 260°C solder bath for 20 seconds.

Heat shrinkage: After being left in an atmosphere of 200'O for 30 minutes, the shrinkage rate with respect to the original size was measured.

Solvent resistance: After dropping a few drops each of toluene, ethyl acetate, and methyl ethyl ketone onto the film-1-, the film was heated for 24 K &'FjM with the lid covered to prevent the solvent from evaporating in an old plate. I observed the condition.

Antistatic property: Immediately after thoroughly rubbing the film with a well-dried cotton cloth, it was evaluated by the degree to which the ash was rubbed when held over cigarette ash.

Transparency: The transmittance of light at 500 nm was measured.

The measured value is film thickness 100. of conversion Displayed as a value.

Glossiness: Reflectance was measured when white light was irradiated at an incident angle of 60°.

Uniformity: The thickness at the edges and center of the film was measured using a thickness gauge, and it was determined whether the variation in thickness was within 10% of the reference thickness.

As is clear from the test results shown in Table 1, the film obtained from the composition of the present invention exhibited various excellent physical properties, but was significantly superior to the film of the comparative example, especially in terms of heat resistance. .

[Effects of the Invention 1 As described above, the composition of the present invention is useful as a constituent material of a film. That is, since the composition of the present invention is easily transformed into a liquid substance by heating, there is no need to dissolve the raw materials in a solvent as is the case in ordinary film manufacturing processes. Therefore, unlike the conventional method, there is no need to provide a solvent removal or recovery process, which simplifies the manufacturing process and reduces manufacturing costs, which is also preferable from the standpoint of pollution control. The composition of the present invention is also excellent in that it can be cured in a very short time by irradiation with active energy rays, heating, or a combination of these operations.

Furthermore, the film obtained from the composition of the present invention has excellent physical properties, especially tear strength, and also has excellent transparency, gloss, and uniformity. There is. In addition to these, the composition of the present invention may contain dyes, pigments, various inorganic fillers, antistatic agents, magnetic powder, antibacterial agents, enzymes, flame retardants, glass peas, plastic powder, wood flour, etc. By blending these blends, it is possible to obtain a film that takes advantage of the characteristics of these blends.

Procedural Supplement 1986! January 1011 Commissioner of the Patent Office Kuro 1H Akira Ml 1, Indication of the case 1985 Patent Application No. 185166 2, Name of the invention Polyurethane (meth)acrylate resin composition 3, Person making the amendment Relationship to the case Patent applicant Name: Nichiban Co., Ltd. 4, Agent 5, Japan-Brazil Voluntary Order for Amendment 6, Opponent of the Amendment “Cepatic acid” described in column 1 of the detailed explanation of the invention in the specification, page 1 O, line 9 of the specification "Correct with sepacic acid J.

2, page 11, line 9 of the specification [r (c) J
is corrected as r (c)J.

3. "(c)" described in page 11, line 11, line 11 of the specification and line 19, line 1] is corrected to r (c) J.

4. In the first line of page 13 of the specification, "the component (B) constituting the component (B)" is replaced with "the component (B) constituting the composition is J."

5. "Made by rICI" stated on page 25, line 5 of the specification is amended to "Merck & Co., Ltd."

6. "Tear strength J" stated on page 35, line 20 of the specification is corrected as heat resistance J.

Claims (1)

[Claims] (1) (A) (a) 100 parts by weight of at least one member selected from the group consisting of di- or triisocyanate of isocyanuric acid derivatives, carbodiimide-modified diphenylmethane diisocyanate, diphenylmethane diisocyanate, and polyisocyanate having a diphenylmethane structure; (b) 10 to 250 parts by weight of at least one selected from the group consisting of low molecular weight compounds containing at least two or more active hydrogens in one molecule, acid anhydrides, and glycidyl compounds with difunctionality or more; and (c) ( 55 to 200 parts by weight of a (meth)acrylic acid derivative having a functional group capable of reacting with meth)acrylic acid or an isocyanate group; 100 parts by weight of a reaction product of (B) isocyanuric acid or a derivative thereof; ) 3 to 40 parts by weight of acrylate, di- or triallyl isocyanurate, or di(meth)acrylate having a bisphenol S-type structure;