JPS634584B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition with excellent air curability suitable for use in paints, adhesives, inks, etc. Conventionally, paints, adhesives, inks, etc. have the property of gradually curing due to oxidation due to oxygen in the air (hereinafter referred to as air curing) when left in the air after evaporating a solvent or water if necessary. Examples of resin compositions or materials of this type that have been used include various synthetic resins mixed with hardening agents such as cobalt naphthenate and lead octylate, oil-modified alkyd resins, and higher fatty acid esters of epoxy resins. , oil-based paints made by adding pigments to oil-based varnishes or drying oils, etc.; however, these have slow air-curing speeds or insufficient hardening, and when used as paints or inks, they do not form a film. It had the disadvantage of poor weather resistance and water resistance. In view of the current state of resin compositions and materials of this type used in the above-mentioned paints, adhesives, inks, etc., the present invention aims to provide resin compositions that can provide films and filled parts with excellent air curability and excellent weather resistance. It was created for the purpose of providing a general formula.

[Formula] (In the formula, R ₁ is H or CH ₃ , R ₂ is

【formula】,

【formula】

[Formula] or

[Formula] R ₃ is H or CH ₃ , m is an integer from 0 to 6, and n is an integer satisfying the following relationship. When m=1, n=2 to 5, m=
For 2 to 6, n=2. ) 1 to 70% by weight of an ester of acrylic acid or methacrylic acid having a cyclic unsaturated group represented by
~30% by weight, 0 to 30% by weight of a compound containing a polymerizable unsaturated group and a hydroxyl group, and 98% by weight or less of a radically polymerizable monomer other than the above as constituent units and a zirconium compound. A resin composition characterized by containing the following. Among the esters of acrylic acid or methacrylic acid having a cyclic unsaturated group used in the present invention, the cyclic unsaturated group is a dicyclopentenyl group.

As a specific example of the ester of [Formula], when m in the above general formula is 0, 8(9)
-Acryloxytricyclo[5.2.1.0 ^2,6 ]-4-decene (this is 8-acryloxytricyclo[5.2.1.0 ^2,6 ]-4-decene and 9-acryloxytricyclo[5.2.1.0 ^{2) ,6} ]-4-decene (the same applies hereinafter), 8(9)-methacryloxytricyclo[5.2.1.0 ^2,6 ]-4-decene (common name, dicyclopentenyl methacrylate), 8(9)-Acryloxytricyclo[5.2.1.0 ^2,6 ]-2-methyl-4-
Decene, 8(9)-Acryloxytricyclo[5.2.1.0 ^2,6 ]-3-methyl-4-decene, 8(9)-
Examples include methacryloxytricyclo[5.2.1.0 ^2,6 ]-2-methyl-decene, 8(9)-methacryloxytricyclo[5.2.1.0 ^2,6 ]-3-methyl-4-decene, etc. When m in the above general formula is 1, 2-
Dicyclopentenoxyethyl acrylate 2-dicyclopentenoxyethyl methacrylate, 2-dicyclopentenoxypropyl (meth)
Acrylate (this means 2-dicyclopentenoxypropyl acrylate and 2-dicyclopentenoxypropyl methacrylate. The same applies hereinafter), 3-dicyclopentenoxyisobutyl (meth)acrylate, 3-dicyclopene Examples include tenoxyneopentyl (meth)acrylate, etc.
When m is 2 to 6, diethylene glycol mono-dicyclopentenyl ether acrylate Diethylene glycol = mono-dicyclopentenyl ether methacrylate, triethylene glycol = mono-dicyclopentenyl ether (meth)
Acrylate, tetraethylene glycol mono-dicyclopentenyl ether (meth)acrylate, pentaethylene glycol mono-dicyclopentenyl (meth)acrylate, hexaethylene glycol mono-dicyclopentenyl ether (meth)acrylate, and the like. Further, as the cyclic unsaturated group possessed by the ester represented by the above general formula, in addition to the zincclopentenyl group, for example,

【formula】,

【formula】,

[Formula] etc., and specific examples when m=0 are 3(4)-acryloxy-1-cyclopentene, 3(4)-methacryloxy-1-cyclopentene, 4(5)-acryloxy-1- cyclohexene,
4(5)-Methacryloxy-1-cyclohexene, 5
(6)-acryloxybicyclo[2.2.1]-2-heptene, 5(6)-methacryloxybicyclo[2.2.1]
Examples include -2-heptene. Among these esters, 8(9)-acryloxytricyclo[5.2.1.0 2,6]-4-decene, 8(9)-acryloxytricyclo[5.2.1.0 ^2,6 ]-4-decene,
(9) -Methacryloxytricyclo [5.2.0 ^2,6 ] -4-
Decene and 2-dicyclopentenoxyethyl (meth)acrylate are particularly preferably used. The ester in which m is 1 to 6 in the above general formula is generally tricyclo[5.2.1.0 ^2,6 ]-3-decenol (common name, dicyclopentenyl alcohol,

[Formula]), tricyclo[5.2.1.0 ^2,6 ]methyl-3-decen-ol

[Formula] cyclopenten-1-ol, 2-methyl-cyclopenten-1-ol, cyclohexen-1-ol, 2-methylcyclohexen-1-ol, bicyclo[2.2.1]
-2- Heptenol, Bicyclo [2.2.1] -3
It is produced by a method in which a product obtained by reacting an alcohol such as -methyl-2-heptenol with ethylene oxide, propylene oxide, etc. is further reacted with (meth)acrylic acid to esterify it. The vinyl copolymer used in the present invention contains the above-mentioned ester in an amount of 1 to 70% by weight (hereinafter, % means % by weight). If it is less than 1%, the air curing properties of the vinyl copolymer will not be expressed,
Moreover, if it exceeds 70%, the weather resistance of the coating formed with the paint or ink obtained from the resin composition will be poor. Furthermore, vinyl copolymers have α and β as structural units.
- Contains unsaturated carboxylic acids in the range of 1 to 30%,
Generally has an acid value of 10-200. The amount of unsaturated carboxylic acid depends on the amount of the compound containing an unsaturated group and a hydroxyl group, which will be described later, but if it is less than 1%, the air curability of the resulting resin composition will be poor, and the adhesion to the coated object will be poor. In addition, the dispersibility of the coloring agent added to the resin composition becomes poor. On the other hand, if the unsaturated carboxylic acid content exceeds 30%, the water resistance of the film obtained from the resin composition will be insufficient. As such α,β-unsaturated carboxylic acids, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid, maleic acid, fumaric acid, etc. are preferably used. Furthermore, the vinyl copolymer may contain a compound containing a polymerizable unsaturated group and a hydroxyl group as a structural unit so as to have hydrophilicity and a nonionic moiety. Specific examples of this unsaturated compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and allyl alcohol. The amount of the unsaturated compound used in the vinyl copolymer depends on the amount of the carboxylic acid, but generally
When it is 30% or more, the water resistance of the film formed by the water-dispersed resin is poor, so it is set to be less than 30%. It is believed that this unsaturated compound improves the storage stability of the coating liquid, similar to the unsaturated carboxylic acid described above, when a pigment or the like is added to the composition of the present invention together with water or a solvent to form a coating liquid. In the present invention, the vinyl copolymer contains, in addition to the above-mentioned ester, α,β-unsaturated carboxylic acid, unsaturated group, and hydroxyl group-containing compound, other suitable radically polymerizable monomers as structural units. % or less. Specific examples of such vinyl monomers include (meth)acrylic acids such as butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate. In addition to alkyl esters and glycidyl (meth)acrylates, styrene, α-methylstyrene,
Examples include alkenylbenzenes such as vinyltoluene, vinyl acetate, vinylpyridine, butadiene, isoprene, chloroprene, acrylonitrile, methacrylonitrile, etc., and these may be used alone or as a mixture of two or more. Since the alkyl ester of (meth)acrylic acid tends to impart adhesive properties to the vinyl copolymer, it is preferably used when the resin composition of the present invention is used as an adhesive. The copolymer may further contain a polyfunctional crosslinking agent such as polyacrylate or diallyl phthalate. The above-mentioned vinyl copolymer can be obtained by copolymerizing each monomer by a conventionally known method, such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, etc. The solvent used in the solution polymerization method is arbitrary as long as the polymerization reaction proceeds smoothly, but it is desirable to use a solvent that dissolves the produced vinyl copolymer, and specific examples include propanol, methyl cellosolve, butyl cellosolve, butyl cellosolve acetate,
Examples include ethyl carbitol, acetone, memethyl ethyl ketone, and ethyl acetate, which may be used alone or in appropriate mixtures. The molecular weight of the vinyl copolymer is appropriately selected depending on the use of the resin composition and is not particularly limited, but the weight average molecular weight is usually 500 to 500,000. If you want to obtain a vinyl copolymer as an aqueous solution or dispersion, it is preferable to add a base to the solution obtained by solution polymerization to neutralize it and then add water, or to produce it from the beginning by an aqueous emulsion polymerization method. . Suitable examples of the zirconium compound in the present invention include organic acid salts such as zirconium octylate, zirconium naphthenate, and zirconium oxalate, oxyacid salts such as zirconium nitrate, halides such as zirconium tetrachloride, tetrabutyl zirconate, Examples thereof include ester coordination complexes such as tetraoctyl zirconate, acetylacetone zirconium salts, and the like, and zirconium octylate and zirconium naphthenate are particularly preferred since they can further improve the air curability of the resin composition. The amount of these zirconium compounds to be used is not particularly limited, but it is usually 0.01 to 10 parts by weight of zirconium metal per 100 parts by weight of the vinyl copolymer, and generally, zirconium compounds are obtained by dissolving the zirconium compounds in a solvent. The solution is added to the vinyl copolymer dissolved or dispersed in a solvent or water. Specific examples of solvents that dissolve zirconium compounds include propanol, methyl cellosolve, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, acetone, methyl ethyl ketone, ethyl acetate, and the like. The reason why the composition of the present invention has excellent air curability is not necessarily clear, but the zirconium compound has a carboxyl group introduced into the vinyl copolymer by the above-mentioned α,β-unsaturated carboxylic acid, etc. tend to combine to form ionic bridges;
On the other hand, since the zirconium compound further promotes the crosslinking reaction in which the above-mentioned cyclic unsaturated groups in the vinyl copolymer are oxidized by oxygen in the air, the vinyl copolymers with increased molecular weights are further crosslinked. Therefore, it is presumed that the resin composition has a high degree of curing. The composition of the present invention may also contain pigments, dyes, viscosity modifiers, tackifying resins, plasticizers, amino resins as curing agents, epoxy resins, isocyanates, etc., depending on the intended use of paints, adhesives, water-based inks, oil-based inks, etc. Conventional additives such as compounds may also be added. The composition of the present invention is usually used in a state in which it is dispersed or dissolved in water or a solvent, applied to the surface of an object to be coated or adhered, dried at room temperature or by heating, and then left at room temperature. It may be used as a heat-melting adhesive by heating and melting it. Since the resin composition of the present invention has the above-mentioned structure, it has a faster curing speed due to air oxidation than resin compositions containing conventional curing agents such as cobalt naphthenate, and therefore is suitable for paints, inks, etc. It has good workability when used in adhesives, etc., and when cured, forms a homogeneous three-dimensional network structure throughout the film when used as a paint or ink, and the entire adhesive layer when used as an adhesive. Therefore, a dry film or dry adhesive layer with excellent water resistance, weather resistance, etc. can be obtained. Examples of the present invention are shown below. Note that parts simply indicate parts by weight. Evaluation of various physical properties was based on the following measurement method. (1) Gel fraction: The dried film was extracted with tetrahydrofuran at room temperature, and the weight of the extracted residue was expressed as a percentage of the original sample weight. (2) Index dryness: A state in which no fingerprints were left on the film when touched with a finger was considered good, and a state in which only a few fingerprints were observed was considered poor. (3) Water resistance: Soak the dried film in water at 20℃ for 10 days.
The condition of the film, such as whitening, blistering, peeling, etc., was observed, and the case where there was no change before and after immersion was evaluated as good. (4) Alkali resistance: The dried film was immersed in a 10% sodium hydroxide aqueous solution at 40°C for 6 hours, and the film was observed for gloss, blistering, and peeling. If there was no change before and after immersion, it was evaluated as good. (5) Weather resistance: irradiated with weatherometer for 500 hours,
The gloss, adhesion, blistering, peeling, and impact resistance of the film were evaluated. A film with a gloss retention rate of 50% or more and no change in performance before and after irradiation was considered good. Example 1 72 parts of 8 (or 9)-acryloxytricyclo[5.2.1.0 ^2,6 ]-4-decene, 31 parts of methacrylic acid
50 parts of butyl methacrylate, 47 parts of 2-ethylhexyl acrylate, and 2 parts of lauryl mercaptan.
A solution obtained by dissolving 8 parts of azoisobutyronitrile was dissolved in 100 parts of butyl cellosolve at 120°C.
The mixture was added dropwise over a period of time, and then stirred for 3 hours to carry out homogeneous polymerization to obtain a vinyl copolymer (A) solution. The weight average molecular weight of the vinyl copolymer was 42,600, the acid value was 100, and the solid content was 67%. This vinyl copolymer solution
Add 150 parts of toluene, 70 parts of toluene, and 25 parts of zirconium octylate (zirconium metal content: 12%), apply it on a steel plate, heat dry at 80℃ for 15 minutes, and form a transparent film with a thickness of 40μ. Obtained. Immediately after heating, the film was dry to the touch and had a gel fraction of 53.6%. The gel fraction after standing for 7 days was 70%.
Water resistance and weather resistance were good. Comparative Example 1 Using the vinyl copolymer (A) obtained in Example 1,
A dry film was obtained in the same manner as in Example 1, except that 7.6 parts of cobalt naphthenate (metal content: 6%) and lead naphthenate (metal content: 20%) were used in place of 25 parts of zirconium octylate. The dryness to the touch immediately after heating was somewhat poor, and the gel fraction was 16%. After standing for 7 days, the gel fraction was 44%, and the water resistance was somewhat poor. Example 2 Using the vinyl copolymer (A) obtained in Example 1,
A dried film was obtained in the same manner as in Example 1, except that 30 parts of zirconium acetylacetonate was used instead of zirconium octylate. Immediately after heating, the film was dry to the touch and had a gel fraction of 48.3%. 7
The gel fraction after being left for a day was 64.2%, showing water resistance and
Weather resistance was good. Example 3 72 parts of 8 (or 9)-acryloxytricyclo[5.2.1.0 ^2,6 ]-4-decene, 20 parts of acrylic acid,
2-ethylhexyl acrylate 28 parts, lauryl methacrylate 20 parts, butyl acrylate 43 parts,
A solution obtained by dissolving 4 parts of lauryl mercaptan and 4 parts of azoisobutyronitrile in 17 parts of ethyl acrylate was added dropwise to 100 parts of butyl cellosolve at 135°C over 3 hours, and then stirred for 3 hours to uniformly polymerize. A vinyl copolymer (B) solution was obtained. The weight average molecular weight of the vinyl copolymer was 19,800 and the acid value was 100. A water-soluble coating liquid was obtained by adding 18 parts of dimethylethanolamine, 100 parts of deionized water, and 20 parts of zirconium naphthenate (metal content: 5%) to the copolymer solution. This was treated in the same manner as in Example 1 to obtain a transparent film on the steel plate. Immediately after heating, the film was dry to the touch and had a gel fraction of 42.0%. 7
The gel fraction after being left for one day was 62.8%, indicating water resistance and
Weather resistance was good. Comparative Example 2 Using the vinyl copolymer (B) obtained in Example 3, 7.6 parts of cobalt naphthenate (metal content 5%) and 7.6 parts of lead naphthenate (metal content 20%) were added instead of zirconium naphthenate. A transparent film was obtained on a steel plate in the same manner as in Example 3 except that Immediately after heating, the dryness to the touch was poor, and the gel fraction was low.
It was 3.8%. Gel fraction after standing for 7 days is 15.0
%, and the water resistance was poor. Example 4 Vinyl copolymer (B) solution obtained in Example 3 300
1 part dimethylethanolamine, 18 parts deionized water
100 parts, zirconium naphthenate (metal content 5%)
20 parts and 85 parts of an aqueous methyl etherified melamine solution (80% non-volatile content) were added to obtain a water-soluble coating liquid. This was applied onto a steel plate and dried by heating at 120°C for 20 minutes to obtain a transparent film with a thickness of 40μ. The dryness to the touch immediately after heating was good, the gel fraction was 97.2%, and the water resistance, alkali resistance, and weather resistance immediately after heating were good.

Claims (1)

[Claims] 1 General formula [Formula] (wherein R ₁ is H or CH ₃ , R ₂ is [Formula], [Formula], [Formula] or [Formula] R ₃ is H or CH ₃ , m is an integer from 0 to 6, and n is an integer that satisfies the following relationship: when m = 1, n = 2 to 5, m =
For 2 to 6, n=2. ) 1 to 70% by weight of an ester of acrylic acid or methacrylic acid having a cyclic unsaturated group represented by
~30% by weight, 0 to 30% by weight of a compound containing a polymerizable unsaturated group and a hydroxyl group, and 98% by weight or less of a radically polymerizable monomer other than the above as constituent units and a zirconium compound. A resin composition comprising: 2. The resin composition according to item 1, wherein the zirconium compound is contained in an amount of 0.01 to 10 parts by weight of zirconium based on 100 parts by weight of the vinyl copolymer. 3. The first material whose ester content of acrylic acid or methacrylic acid in the vinyl copolymer is 5 to 50% by weight.
The resin composition according to item 1 or 2. 4. Items 1 to 4, wherein the ester of acrylic acid is 8-acryloxytricyclo[5.2.1.0 ^2,6 ]]-4-decene or 9-acryloxytricyclo[5.2.1.0 ^2,6 ]4-decene. The resin composition according to any one of item 3. 5 The ester of methacrylic acid is 8-methacryloxytricyclo[5.2.1.0 ^2,6 ]-4-decene or 9-
The resin composition according to any one of items 1 to 3, which is methacryloxytricyclo[5.2.1.0 ^2,6 ]-4-decene.