NL7906873A - PHOTOGRAPHY RESIN COMPOSITIONS. - Google Patents

Description

Jk 49 305 / Bos / AS _i,

Hitachi Chemical Company, Ltd., of Shinjuku-ku, Tokyo, Japan.

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I Photo-curable resin compositions. ;

The invention relates to photo-curable resin compositions with superior water resistance. In recent years, the use of photo-curable resins i for curing coating films by means of I

5 of irradiation with light at normal temperature and with! I attracted public attention at high speed, instead of i thermally hardening or hardening at normal

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j temperature by drying for a long time J I period. In the meantime, coating paints for external building materials, such as roof tiles, slates, colored zinc plate, aluminum frames and plastic board, are required. that they show good appearance and resistance to shooting and good weather resistance and water resistance. To coating paints for internal building materials, such as materials for walls, floors, ceilings, furniture, j j; .j and the like, for example asbestos cement-calcium silicate- j ΐ j! plate, asbestos slate plate, masonry cement, clay plate, plastics, wood materials, paper materials and the like, are also required to have good appearance, resistant to fading and excellent water resistance, anti-staining property and have resistance to solvents. To date, the stoving-type paints have been used to meet these requirements. However, problems remain that a large amount of thermal energy is required for stoving, that there is a tendency for uneven hardness to occur.

becoming of the coating film due to scattering I i I

I of thermal conductivity to the material and that one! ! long treatment time is required for such processes as j.

j ______; ______; ______ i 7906873 -2 - * t. --------- -------- -------- ------ I_______ ...... "j heating, raising the temperature and cooling down. In the present invention, the above-mentioned problems are overcome and photo-curable resin compositions are provided with superior water resistance by curing a coating film at normal temperature for a short period of time.

The invention therefore relates to photo-; curable resin compositions consisting of (a) at least one compound selected from acrylic or methacrylic esters of an epoxy compound having not less than two epoxy groups in the molecule and isocyanate-modified epoxy esters obtained by reaction of the acrylic or methacrylic ! ester of the epoxy compound with a polyisocycnate in one! such amount that the equivalent ratio of the NCO groups to the OH groups does not exceed 1; ? (b) a photopolymerizable monomer that is copolymerizable with the component (a); (c) a polyisocyanate compound; (d) a photosensitizing agent; and (e) a sensitizing excipient, wherein the amounts of the components (a) to (e) are as follows: 0/100 = (b) / ((a) + (b)) = 70/100 (wt . ratio) 1/100 = (c) / ((a) + (b)) = 50/100 (weight ratio) 0.5 / 100 = ((d) + (e) / ((a) + ( b)) = 15/100 (weight ratio) j 0/1 = (e) / (d) = 3/1 · (molar ratio) j

The above epoxy compounds are compounds having no less than two epoxy groups in the molecule, such as diglycidyl ethers obtained by reaction of bisphenols, for example bisphenol A, or hydrogenation products thereof with epichlorohydrin, di-glycidyl esters, which are obtained by reaction of aromatic dicarboxylic acids or hydrogenation products thereof with epihalohydrins, and polyglycidyl ethers obtained by reaction of alkane polyalcohols with epichloro-790 68 73-3-9 hydrine. It is preferred that the epoxy equivalent ranges from 100 to 1500, more preferably from 140 to 1000. The compounds can be used alone or in combination.

The above acrylic or methacrylic esters of the epoxy compounds can be obtained by ester addition reaction of the above epoxy compounds with acrylic or methacrylic acid. The reaction can be carried out! by mixing an epoxy compound with acrylic or methacrylic acid such that the equivalent ratio of epoxy group / carboxyl group will be 1 / 0.5-1 / 1, preferably 1 / 0.8-1 / 1! and by heating the mixture at 60-120 ° C when present; an alkaline catalyst to produce an acid value of 0-20, according to a conventional method. The acrylic or methacrylic esters of epoxy compounds thus obtained are polyhydroxy compounds containing hydroxyl groups.

The isocyanate-modified epoxy esters fully

According to the invention can be obtained by reaction 20! of the epoxy ester, which is a polyhydroxy compound, with I.

a polyisocyanate, the acrylic or methacrylic esters of the epoxy compound being intermolecularly linked to the polyisocyanate such that the polymerization can be sufficiently carried out. In this reaction, the molecular weight 25 weight distribution is adjusted by varying the amount of polyisocyanate to be used. The reaction can be carried out, according to a conventional method, in the absence or presence of a catalyst such as tin compounds, for example dibutyltin dilaurate, dibutyltin-2-30 ethylhexaoate or dibutyltin diacetate, at 20-80 ° C, by adjust the equivalent ratio of isocyanate (NCO) groups in a polyisocyanate compound against hydroxyl (OH) groups in an acrylic or methacrylic ester of an epoxy compound so that they do not exceed 1, preferably 0.2 to 35 -1, most preferably 0.3 to 0.7. More than

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* 7906873 - 4 * 1 equivalent ratio of NCO groups / OH groups will not yield highly polymerized compounds and will not leave a group reacting with NCO groups. An equivalent ratio of less than 0.2 / 1 will not yield highly polymerized compounds, causing poor curing. 1

In order to obtain a sufficiently high polymer and leave enough OH groups to react with NCO groups in the component (c), the equivalent ratio of NCO groups in the polyisocyanate / OH groups in the acrylic or methacrylic esters of the epoxy compound is preferably 0.3 / 1 to 0.7 / 1. j

As the polyisocyanate, for example, are listed; toluene diisocyanate, xylene diisocyanate, hexamethyl-15-lene diisocyanate, isophorone diisocyanate, lysine diisocyanate,

2,2,4-trimethylhexamethylene diisocyanate, cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, isopropylidene bis (4-cyclohexyl isocyanate) and hexamethylene diisocyanate / biuret. Also connections can be included which are; Formed by reacting the above polyisocyanates with a polyalcohol, such as propanediol, butanediol, hexane diol, polyethylene glycol, trimethylol propane and pentaerythritol, with a portion of, preferably, not less than I

two remaining isocyanate groups in one molecule. The photo-curable resin compositions of the invention may, if necessary, contain a photopolymerizable monomer (b) together with the component (a) as the photopolymerizable component. Such photopolymerizable monomers (b) include, for example, acrylic esters; Such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, cyclohexyl acrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, butanediol diol. acrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate and trimethyl propane triacrylate; and methacrylic esters, such as methyl methacrylate, ethyl methacrylate, butyl | 7906873 * - 5 - Methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, butanediol dimethacrylate, neopentyl dimethacrylate, polyethylene glycol dimethacrylate, and trimethylol-5-methyl. In addition, oligomers, such as urethane acrylate, polyester acrylate and the like, can be included as the photopolymerizable ingredients. The 1-urethane acrylate means a relatively low molecular weight compound which can be obtained by reacting hydroxyalkyl acrylate or methacrylate with the above acrylic or methacrylic acid and which has photopolymerizable unsaturated bonds. The polyester acrylate means a compound obtained by reaction of acrylic or | methacrylic acid with a hydroxyl-containing polyester

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Oligomer, which can be obtained by the reaction of a polybasic acid, such as phthalic acid, hexahydrophthalic acid, adipic acid, sebacic acid and the like, with a polyhydric alcohol such as ethylene glycol, propylene glycol, butane diol, an oxyalkylene glycol, dimethylol propane and such 20; The amount of the photopolymerizable monomer to be used in the process according to the invention will vary from i | 0 to 70% by weight, preferably 30 to 50% by weight, based on the total weight of the photopolymerizing file. part. Use of more than 70% by weight of the photopolymer sable monomer will reduce the properties of the coating film as a whole, which is obtained when the photo! curable composition is applied to coating materials; j materials, deteriorate. j

Preferably, the above photopolymerizable component has no carbon-carbon unsaturated double bonds other than the photopolymerizable carbon-carbon unsaturated bonds in the respective molecules. In other words, when the compounds with no unsaturated compounds other than the photopolymerizable compounds are used, they are useful as coating materials for exterior building materials especially due to the fact that such connections have superior weather resistance.

The polyisocyanate compounds (c) used in the process of the invention may include the above polyisocyanate. j

The amount of polyisocyanate compounds (c) to be used ranges from 1 to 50 parts by weight, preferably from 3 to 20 parts by weight, based on 100 parts by weight of the photo-polymerizable component. The use of less than 1 part by weight of the polyisocyanate compound cannot improve the water resistance. On the other hand, the use of more than 50 parts by weight thereof adversely affects the film properties. When the photopolymerizable components have sufficient OH groups, ie, in cases where the equivalent ratio of NCO groups in the polyisocyanate compound (c) / OH groups in the photopolymerizable components is between 0.2 / 1 and 1/1, the water resistance may be 20 are noticeably improved.

The photo-curable resin composition of the invention may contain a photosensitizing agent, or a photosensitizing agent and a sensitizing adjuvant. The sensitizing agent includes carbonyl compounds such as benzophenol, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzil, diacetyl, acetophenone and anthraquinone. Sulphides and ·; ï

halides. The sensitizing excipient includes J

alkyl and alkanolamines, such as triethylamine, 2-dimethyl-j (30 aminoethanol, N-methyl diethanolamine, triethanolamine, 3-dimethylamino-1-propanol and 2-dimethylamino-2-methyl-1-propanol. The sensitizers are used alone | or in combination with sensitizing excipients Amount of photosensitizing agents to be used 35 j alone or of photosensitizing agents and sensitive 5 7 ..... 7906873 9 _ 7_ adjuvants , will range from 0.5 to 15 wt%, preferably 2 to 8 wt%, based on the weight of the photopolymerizable ingredients It is preferred that the ratio of the sensitizing excipient until the photosensitizer is between 0/1 and 3/1: When used in an amount of more than 3 moles per mole of the photosensitizer, this means wastage. The sensitizer excipient is preferably used in a amount of not less than 0.3 moles per mole of the photo data dusting material, so that! j play a sufficient role. j i

The photo-curable resin compositions of the invention may further contain various additives, for example, polymers such as ketone resins, acrylic resins, polyester resins, polyethylene, polypropylene and; | polyvinyl acetate; pigments such as titanium white, spherical or Ι plate-like fillers that reflect or transmit light, such as aluminum powder, mica, talc and kaolin; plasticizers | such as diallyl phthalate; and dyes to achieve their own-20; improve shelves. ] i j j The invention is further explained to the = * j! using the following examples and comparative examples .;

j · Example I. I

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In a reaction vessel, 192 parts by weight of hydrogenated bisphenol A type diglycidyl ether were added with a ! epoxy equivalent of 240 (Adeka Resin EP-4080, trademark i -? of Asahi Denka Kogyo KK), 192 parts by weight of diglycidylhexa hydrophthalate with an epoxy equivalent of 160 (Showdine 540, j trademark of Showa Denko KK), 144 parts by weight of acrylic acid 30 parts by weight of triethylamine and 0.1 parts by weight of hydroquinone were added and the mixture was heated up. 90-100 ° C for j | about 15 hours with stirring to obtain an acid compound (epoxy acrylate) with an acid number of 10. To the vessel were then added 500 parts by weight diethylene glycol dii 35 L acrylate to obtain a homogeneous solution]

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7906873-8 and then 100 parts by weight of methyl ester of lysine isocyanate (lysine isocyanate M-100, trademark of Toray Industries, Ine *) was added dropwise at 60 ° C.

The mixture was heated under stirring for 6 hours and the reaction continued until isocyanate groups disappeared. The equivalent ratio of OH groups of the epoxy esters to the NCO groups of the polyisocyanates (OH / NCO) was 1 / 0.49. 200 parts by weight of the polyisocyanate compound (the compound obtained by reacting 1 mole of trimethylol propane with 3 moles of hexamethylene diisocyanate, NCO content 12.8% by weight, Colonate HL, trademark of Nippon Polyurethane, were added to the resin solution thus obtained. Kogyo KK, polyisocyanate solids content 75 wt%); 50 parts by weight of a ketone resin (Hilac 222, trademark of Hitachi Chemical Co. Ltd.), 50 parts by weight benzophenone and 30 parts by weight of dimethylaminoethanol was added, whereby a photo-curable resin composition was obtained. The equivalent! spring ratio of OH groups in the photopolymerizable component to NCO groups in the polyisocyanate compound 20 (OH / NCO) was 1 / 0.63.

Example II. .

According to the same procedure as described in Example I, 192 parts by weight of a diglycidyl ether of the hydrogenated bisphenol A type J 25 with an epoxy equivalent of 240 (Adeka Resin EP-4080, trademark of Asahi Denka Kogyo KK), 192 were reacted. parts by weight. ) diglycidyl hexahydrophthalate with an epoxy equivalent of 160! (Showdine 540, trademark of Showa Denko. K.K.), 144 wt. | parts of acrylic acid, 1 part by weight of triethylamine and 0.1 part by weight of hydroquinone. The mixture thus obtained was dissolved in 400 parts by weight of diethylene glycol diacrylate and trimethylol propane triacrylate. To the mixture were further added 50 parts by weight of a ketone resin (Hilac 222, trademark of Hitachi Chemical Co. Ltd.), 300 parts by weight of the polyiso-35-cyanate compound (Colonate HL, trademark of Nippon 7906873). 9-

Polyurethane Kogyo K.K., solids content 75 wt%), 50 parts by weight of benzophenone and 30 parts by weight of dimethylaminoethanol, whereby a photo-curable resin composition was obtained. ; ; The equivalence ratio of the OH groups in the photopolymerizable component to the NCO groups in the polyisocyanate compound (OH / NCO) was 1 / 0.48.

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Example III.

Following the same procedure as in Example II except that the ketone resin was not used, a photo curable resin composition was obtained.

Example IV. ! | A mixture of 136 parts by weight of a diglycidyl ether of the bisphenol A type with an epoxy equivalent of 170 (Epikote 828, trademark of Shell Chemical Co. Ltd./, 15 240 parts by weight of diglycidyl phthalate with an epoxy equivalent of 200 (Showdine 508, trademark of Showa Denko KK), I 144 parts by weight acrylic acid, 1.0 parts by weight triethylamine and 1

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0.1 part by weight of hydroquinone, was heated to 90 DEG-100 DEG C. for 15 hours with stirring, whereby a compound having an acid number of 10 was obtained. The compound was treated entirely in the same manner as in Example I, leaving a s j; photo-curable resin composition was obtained. j j Example V. |

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By the same procedure as in Example 1, j, except that 100 parts by weight of tolylene diisocyanate were obtained. Using 1 instead of lysine diisocyanate, a photo was taken. ; curable resin composition obtained.

The equivalent ratio of the OH groups in the epoxy esters to the NCO groups in the polyisocyanate (OH / NCO) i i

30 was 1 / 0.60 and the equivalent ratio of the OH groups in I.

ï the photopolymerizable component into the NCO groups!

1 the polyisocyanate compound (OH / NCO) was 1 / 0.79. I

• Comparative example 1. | The procedure was followed from example I, except that the ketone resin (Hilac 222) and the polyisocyanate compound

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7 9 δ 6 8 7 3 ΙΟΙ ____ .____ (Colonate HL) were not used to obtain a photo-curable resin composition.

Comparative example 2.

The procedure was followed from Example 2, 5 except that the ketone resins (Hilac 222) and the polyisocyanate compound (Colonate HL) were not used to obtain a photo-curable resin composition. !

Each of the compositions obtained in the! Examples I-III and Comparative Examples 1 and 2 were applied as a 50 µm thick coating on a flexible board, which was irradiated with ultraviolet light for curing, thereby obtaining a sample. The results of a number of tests carried out j 'are summarized in the table. j i

15 TABLE. I

Curing-1 ^ Pencil- ^ Water Resistance Heat- ^ I

property hardness ^ 3) kdcend4) cycle (secJ water water

Example I 3 H o o o Example II 5 H o o o

Example III 5 H o o o J

Example IV 3 H o o o | .

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Example V 3 H o o o j i i

Comparative example 3 H x x x 25 Comparative example 2 5 H x x x <1 __ y - S | , __ 7906873 _11_

Test 1: Each panel was placed 10 cm away from a 2 kW (80W / cm) high pressure mercury lamp.

The time from the start of the ultraviolet light irradiation to the touch dry sensation with a finger was measured. ;

Trial 2: Mitsubishi pencil Uni was used. 1

Test 3: Each test piece was immersed in warm water at 40 ° C for 20 days, o: nothing extraordinary.

10 x: change (turned white). ! 4 y

Trial 4; Each test piece was immersed in boiling water! i for 2 hours. ! o: nothing extraordinary, x: change (turned white).

Experiment 5: Heat cycle (at -20 ° C for 3 hours - at 80 ° C for 3 hours - at room temperature for 18 hours) was repeated 20 times, o: nothing extraordinary.

x: change (occurrence of swelling or cracks).

The test pieces obtained using the compositions of Examples I-V had excellent gloss. As a result of an outdoor exposure test for 1 month, the test specimens according to Examples m-m showed nothing extraordinary, while those according to Examples IV and V turned yellow. j

From the above, it will be appreciated that the photo-curable resin compositions of the invention have superior water resistance and also have superior weather resistance when they have no unsaturated bond other than a photopolymerizable unsaturated bond.

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7906873 - 1 - 2 - s have saturated bond in the photopolymerizable component. The photo-curable resin compositions according to the invention are particularly suitable for paints for building materials such as roof tiles, slates, colored zinc plate, aluminum frames, plastic board and wood.

j r i j! \ i "j i j | * _ Conclusions.

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7906873

Claims (4)

1. Photo-curable resin composition, consisting of I (a) at least one compound selected from acrylic or methacrylic esters of an epoxy compound with non | Less than two epoxy groups in the molecule and an isocyanate-modified epoxy ester obtained by reaction of the acrylic or methacryl ester of the epoxy compound with a polyisocyanate in such an amount that the ratio of the NCO groups to the OH groups do not; is more than 1; j i (b) a photopolymerizable monomer that can be copolymerized with the component (a); ; (c) a polyisocyanate compound; j (d) a photosensitizing agent; and ^ 5 (e) a sensitizing excipient, J wherein the amount of components (a) to (e) is as follows: 0/100 = (b) / ((a) + (b) = 70/100 ( weight ratio) 1/100 = (c) / ((a) + (b).) = 50/100 (weight ratio) 20 0.5 / 100 = ((d) + (e)) / (( a) + (b)) = 15/100 (weight ratio) 0/1 ^ (e) / (d) = 3/1 (molar ratio). Photo-curable resin composition according to claim 1, characterized in that the amounts of the components (a) to (e) are as follows: 30/100 = (b) / ((a) +) (b)) = 50/100 (weight ratio) 3/100 = (c) / ((a) + (b)) - 20/100 (weight ratio) 2/100 = ((d) + (e )) / ((a) + (b)) = 8/100 (weight ratio) 0.3 / 1 = (e) / (d) = 3/1 (molar ratio). i i i L________________i 790 6873 —14_ c • 9 Photo-curable resin composition according to claim 1 or 2, characterized in that the equivalent ratio of the NCO groups in (c) to the OH groups in (a) and (b) is as follows: | 0.2 / 1 = NCO / OH = 1/1. j j Photo-curable resin composition according to any one of claims 1 to 3, characterized in that the components (a) and (b) are not carbon-carbon unsaturated! bonds have carbon-unsaturated bonds other than photopolymerizable carbon. j i i i "7906873