JPH0442411B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photopolymerizable curable composition with excellent heat resistance, adhesion and curing properties. More specifically, carboxylic acid residues and/or glycidyl ester compound residues and/or glycidyl ester compound residues containing an ethylenically unsaturated group having chain polymerizability via the oxygen of the phenolic hydroxyl group of vinylphenol or halogenated vinylphenol. The present invention relates to a photocurable composition comprising a polymer containing vinylphenol and/or halogenated vinylphenol units into which an ether compound residue has been introduced. In recent years, energy conservation has been emphasized in all industrial sectors, and energy conservation has also become an essential issue in the field of resin processing. In particular, the heat curing method conventionally used in resin processing is problematic because it usually requires high temperatures and long periods of time, and it also has drawbacks such as being a source of pollution due to the generation of toxic volatiles. Therefore, improvement is strongly desired. On the other hand, in the photocuring method using light irradiation such as ultraviolet rays, in addition to completing the reaction in a short time at room temperature, (a) the curing reaction can be carried out at a low temperature, so there are fewer emissions of environmental pollutants, and there is no residual residue in the cured product. Distortion is also small; (b) since the reaction is substantially initiated by light, there is no need to add any initiator, and contamination of the cured product by the initiator is prevented; and (c) if light irradiation is stopped. Since the reaction is stopped, it has various advantages such as the degree of curing can be easily controlled without requiring special energy. In particular, photocuring methods are easy to apply in fields such as paints, coatings, and adhesives, and in the coming energy-saving era, there is a strong desire for the emergence of better photocurable materials. In order to meet these various demands, the present inventors have conducted extensive research into novel photocurable compositions, and have found that, through the oxygen of phenolic hydroxyl groups such as vinylphenol and halogenated vinylphenol, A polymerizable product containing a vinylphenol and/or halogenated vinylphenol unit into which a carboxylic acid residue and/or a glycidyl ester compound residue and/or a glycidyl ether compound residue containing an ethylenically unsaturated group having chain polymerizability is introduced. It has extremely excellent curing properties, and if necessary, by adding an ethylenically unsaturated compound or a curing accelerator, a cured product with a fast curing speed and excellent heat resistance and adhesion can be obtained. They found this and completed the present invention. That is, the gist of the present invention is that the formula () (In the formula, R ¹ represents a chain polymerizable ethylenically unsaturated alkyl group having 2 to 4 carbon atoms, X represents a halogen atom, and n represents an integer of 0 to 2.) Vinylphenol unit in which the hydrogen of the hydroxyl group is substituted with a carboxylic acid residue having an unsaturated alkyl group, formula () (In the formula, R ² represents a chain polymerizable ethylenically unsaturated alkyl group having 2 to 4 carbon atoms, X represents a halogen atom, and n represents an integer of 0 to 2.) A vinylphenol unit in which the hydrogen of the hydroxyl group is substituted with a glycidyl ester compound residue having an unsaturated alkyl group, and the formula () (In the formula, R ³ represents a chain polymerizable ethylenically unsaturated alkyl group having 2 to 4 carbon atoms, X represents a halogen atom, and n represents an integer of 0 to 2.) 10 mol% as an essential constituent unit of at least one vinylphenol unit in which the hydrogen in the phenolic hydroxyl group is selected from vinylphenol units in which the hydrogen in the hydroxyl group is substituted with a glycidyl ether compound residue having an unsaturated alkyl group. Contains the proportion above, and the remainder is expressed by the formula () (In the formula, X represents a halogen atom, and n is 0 to 2
represents an integer. ) and/or at least one comonomer unit selected from styrene units, α-methylstyrene units, methyl vinyl ether units, and ethyl vinyl ether units; When the photocurable composition is composed of more than one kind of structural units, each of the structural units is randomly bonded, and the photocurable composition is composed of a polymer having a degree of polymerization of 5 to 500. In the photocurable composition of the present invention, the vinylphenol unit may be an ortho, meta, or para isomer, and a portion of the hydrogen other than the hydrogen contained in the hydroxyl group may be substituted with a halogen. It's okay. Next, the carboxylic acid residue having an unsaturated alkyl group in the unit represented by the formula () is:
It is a residue in which a linear or branched unsaturated carboxylic acid having 3 to 5 carbon atoms reacts with a phenolic hydroxyl group to form an ester bond. Typical examples of these are acrylic acid, methacrylic acid, and crotonic acid. , isocrotonic acid, vinyl acetic acid, α-methyl crotonic acid, α-ethyl acrylic acid, β-methyl crotonic acid, 4-pentenoic acid, and the like.
In addition, the glycidyl ester compound residue having an unsaturated alkyl group in the unit represented by the above formula () refers to the glycidyl ester compound formed from the above carboxylic acid and glycidyl alcohol reacting with a phenolic hydroxyl group to form an ether bond. The glycidyl ether compound residue having an unsaturated alkyl group in the unit represented by the formula () is, for example, vinyl alcohol,
It is a residue in which a glycidyl ether compound formed from an unsaturated alcohol such as allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, and glycidyl alcohol reacts with a phenolic hydroxyl group to form an ether bond. Next, the unsaturated carboxylic acid residue is introduced into the vinylphenol unit by a known method, for example, by converting the unsaturated carboxylic acid into an acid chloride, and then reacting this with a sodium salt of the vinylphenol unit. easily achieved. The above-mentioned glycidyl ester compound residues and glycidyl ether compound residues can also be introduced by known methods, for example, by reacting the above-mentioned glycidyl ester compounds or glycidyl ether compounds with vinylphenol units using a tertiary or quaternary amine as a catalyst. This can be easily achieved by
Introduction of these residues can be easily carried out whether the vinylphenol or halogenated vinylphenol is in the form of a monomer or a polymer. Therefore, the polymer constituting the photocurable composition of the present invention can be prepared by homopolymerization of monomers into which these residues are introduced or by copolymerization of products into which various residues are introduced. can. Furthermore, during such copolymerization, other vinyl monomers such as styrene, α-
It may be copolymerized with methylstyrene, methyl vinyl ether, etc. in an appropriate ratio. In addition, when a homopolymer of vinylphenol and halogenated vinylphenol or a copolymer with other vinyl monomers as described above is prepared in advance and the above residues are introduced into the homopolymer, two or more types of residues may be introduced. They can also be mixed and introduced in an appropriate ratio. Next, an example of a polymer constituting the photocurable composition of the present invention is shown in formula (). When this polymer is a copolymer, each structural unit is generally randomly bonded. There is. Further, the degree of polymerization of this polymer is generally 5 to 500. In formula (), R ¹ , R ² and R ³ have 2 carbon atoms
-4 represents an unsaturated alkyl group, and R ⁴ represents a substituent such as a phenyl group or a methoxy group. X represents a halogen, and n represents an integer of 0 to 2. Furthermore, a,
The composition ratios indicated by b, c, x, and y can be set freely by selecting the reaction conditions, but in the present invention, the polymer is cured by ultraviolet rays or the like to make it insoluble in the solvent. (a+b+c)/
It is necessary that the value of (a+b+c+x+y) is 0.1 or more, and a range of 0.2 or more is practically preferable. Next, although the curing reaction of the composition of the present invention can be carried out using only the polymer shown in formula (), it is usually carried out in combination with a curing accelerator. This curing accelerator can be broadly classified into thermal curing accelerators and photocuring accelerators (photosensitizers), and any of these known ones can be used in the present invention. Examples of these photocuring accelerators include hydrogen peroxide, peroxides such as benzoyl peroxide, organic carbonyl compounds such as diacetyl, benzophenone, benzoin, ω-bromoacetophenone, chloroacetone, benzoquinone, anthraquinone, and diphenyl. Disulfide, dibenzyl sulfide, tetraethylthiuram disulfide, methyldithiocarbamate,
Organic sulfur compounds such as mercaptan, azobisisobutyronitrile, 2,2'-azobispropane,
Azo compounds such as hydrazine, metal carbonyls such as Mn ₂ (CO) ₁₀ , organometallic compounds such as tetraethyl lead, Fe ³⁺ , Sn ²⁺ , Ag ⁺ , Ce ²⁺ , ClO ₂ ²⁺ ,
Examples include inorganic ions such as [Co(NH ₃ ) ₅ Cl] ²⁺ , and pigments such as methylene blue, eosin, riboflavin, and thionin. Among these, benzoyl peroxide, benzophenone, benzoins, diphenyl disulfide, dibenzyl disulfide, diacetyl, benzyl and the like are particularly preferably used in the present invention. In addition, in order to impart special performance to the cured product obtained by curing the composition of the present invention or to adjust various operations, other known polymers may be added to the polymer constituting the composition of the present invention. A photocurable material may also be added. Examples of this photocurable material include linear or branched unsaturated carboxylic acids having 3 to 18 carbon atoms or linear or branched unsaturated alcohols having 2 to 18 carbon atoms. Furthermore, esters or amide compounds of polyhydric alcohols such as trimethylolpropane and pentaerythritol and unsaturated carboxylic acids such as acrylic acid or methacrylic acid, allyl compounds such as diallyl phthalate and triallyl cyanurate, styrene, acrylonitrile, N Examples include vinyl compounds such as vinylpyrrolidone and drying oils such as linseed oil and tung oil, which have an iodine value of 110 to 185 according to the Wyss method. The method of curing the novel photocurable composition according to the present invention is not limited to the photopolymerization method, and it is also possible to cure it simply by heating, or by adding a radical generator and curing at room temperature or by heating. However, in particular, when using a photocuring reaction, the curing time is shorter than that of conventionally known methods even when carried out at a low temperature below room temperature, and the resulting cured product has significantly superior heat resistance and adhesion. It has the characteristic of being The present invention will be specifically explained below with reference to Examples. Example 1 Polyparavinylphenol (manufactured by Maruzen Petrochemical Co., Ltd., trade name "Maruka Linker M": weight average molecular weight 5000, number average molecular weight 2500, degree of polymerization approx.
21) A mixed solvent containing 20 g of glycidyl methacrylate, 0.7 g of triethanolamine, and 100 g of methyl ethyl ketone was heated under reflux for 5 hours with stirring to carry out a reaction. Next, the precipitate produced by mixing this reaction solution with a large amount of water was filtered off, dried, and subjected to structural analysis using infrared absorption spectroscopy and nuclear magnetic resonance spectroscopy. As a result, it was estimated that the precipitate was a polymer as shown by formula (). Note that the form of the polymer represented by formula () is a form in which each unit is randomly bonded. Example 2 6.0 g of ortho-vinylphenol, 6.0 g of para-vinylphenol and 100 g of methyl methacrylate
The mixture was heated to 70° C. in the presence of zinc acetate and reacted for 2 hours while removing the methanol produced. After that, the reaction mixture was heated at 35°C under reduced pressure to remove low-boiling substances using a rotary evaporator, and the residue was analyzed and found to be a mixture consisting of 42% by weight of vinylphenol and 58% by weight of methacrylic acid ester of vinylphenol. It was hot. Next, 10 g of this mixture and 2 g of ethyl vinyl ether were dissolved in methylene chloride, and a polymerization reaction was carried out at -78 DEG C. for 20 hours using boron trifluoride etherate as an initiator. As a result of analyzing the structure of the polymer obtained by removing the terminal reactants from this reaction product, it was estimated to be a random polymer represented by the formula (). Example 3 Brominated poly paravinylphenol unit (manufactured by Maruzen Petrochemical Co., Ltd., trade name "Maruka Linker MB": weight average molecular weight 6200, number average molecular weight
3000, degree of polymerization of about 13), 9.5 g of allyl glycidyl ether, 2 g of tetramethyl ammonium bromide and 150 g of methyl isobutyl ketone was heated to reflux with stirring and reacted for 5 hours. Next, the precipitate produced by mixing this reaction solution with a large amount of benzene was filtered, dried, and subjected to structural analysis. As a result, it was estimated to be a random polymer represented by the formula (). Furthermore, when this polymer was mixed with the same weight of diallyl phthalate, they were easily compatible and a uniform solution was obtained. Example 4 Polymers obtained in Examples 1-2 and Example 3
Regarding the mixture of the polymer and diallyl phthalate obtained in step 1, 0.5 g of each polymer and mixture and 25 mg of benzoin isopropyl ether were dissolved in 5 ml of methyl ethyl ketone to prepare three types of photopolymerizable composition solutions. Next, after pouring these solutions onto an aluminum plate, the solvent was evaporated to form a photocurable composition film.
The table shows the results of irradiating light from a distance of 30 cm using a 450W high-pressure mercury lamp and measuring the irradiation time until the film no longer dissolves in methyl ethyl ketone. Further, even when the thus obtained cured film was heat-treated in a constant temperature bath at 120° C. for 1 hour, no abnormality in appearance such as cracking or peeling was observed. 【table】

Claims (1)

[Claims] 1 Formula () (In the formula, R ¹ represents a chain polymerizable ethylenically unsaturated alkyl group having 2 to 4 carbon atoms, X represents a halogen atom, and n represents an integer of 0 to 2.) Vinylphenol unit in which the hydrogen of the hydroxyl group is substituted with a carboxylic acid residue having an unsaturated alkyl group, formula () (In the formula, R ² represents a chain polymerizable ethylenically unsaturated alkyl group having 2 to 4 carbon atoms, X represents a halogen atom, and n represents an integer of 0 to 2.) A vinylphenol unit in which the hydrogen of the hydroxyl group is substituted with a glycidyl ester compound residue having an unsaturated alkyl group, and the formula () (In the formula, R ³ represents a chain polymerizable ethylenically unsaturated alkyl group having 2 to 4 carbon atoms, X represents a halogen atom, and n represents an integer of 0 to 2.) 10 mol% as an essential constituent unit of at least one vinylphenol unit in which the hydrogen in the phenolic hydroxyl group is selected from vinylphenol units in which the hydrogen in the hydroxyl group is substituted with a glycidyl ether compound residue having an unsaturated alkyl group. Contains the proportion above, and the remainder is expressed by the formula () (In the formula, X represents a halogen atom, and n is 0 to 2
represents an integer. ) and/or at least one comonomer unit selected from styrene units, α-methylstyrene units, methyl vinyl ether units, and methyl vinyl ether units; A photocurable composition comprising a polymer in which each of the structural units is randomly bonded and has a degree of polymerization of 5 to 500 when it is comprised of more than one type of structural unit. 2. The photocurable composition according to claim 1, which contains a curing accelerator. 3. The photocurable composition according to claim 1, which contains an ethylenically unsaturated compound. 4. The photocurable composition according to claim 1, which comprises a curing accelerator and an ethylenically unsaturated compound.