JPH06100610A - Production of polymer, composition containing the polymer, and polymer derived from the composition - Google Patents

Abstract

PURPOSE:To provide the method by which a polymer having two or more hy droxyl groups at one end and at least one hydroxyl group at the other is effi ciently and easily obtained at low cost from a wide range of vinyl monomers; to provide a composition containing the polymer; and to provide a polymer derived from the composition. CONSTITUTION:A vinyl monomer (a) is polymerized in the presence of alcohols (b) comprising a polyhydric alcohol as an essential ingredient using an initiator system (c) comprising hydrogen peroxide as an essential ingredient substantially in the absence of any substance other than the ingredients (a), (b), and (c) to thereby obtain a polymer. This polymer is used as an essential ingredient to prepare a composition. A polymer is derived from the composition.

Description

Detailed Description of the Invention

[0001]

This invention relates to a method for producing a useful polymer having hydroxyl groups capable of reacting with various functional groups at both ends and at least two hydroxyl groups at at least one terminal. It relates to compositions containing said polymers and their uses, as well as polymers derived from said compositions.

[0002]

2. Description of the Related Art A polymer having hydroxyl groups at both terminals is prepared by reacting the hydroxyl groups at the above terminals by an appropriate method.
It can be easily converted to another functional group, and the reactivity of the hydroxyl group at the terminal is utilized to linearize and / or network by reacting the hydroxyl group by an appropriate method, and as a result, The polymer compound has various excellent physical properties such as strength, heat resistance, weather resistance, and durability.

This polymer having hydroxyl groups at both ends is
By exhibiting the characteristic of having hydroxyl groups at both ends, for example, the following great advantages are obtained. When used as various resin raw materials (crosslinking agent etc.) such as polyester resin, polyurethane resin, polycarbonate resin,
Since there are no unreacted substances that impair the physical properties of the material, it is ensured that all polymers are incorporated into the resin crosslinked structure.

There is no free chain at the end of the polymer as in the case of using a copolymer of a vinyl monomer having a functional group, that is, there is no play part which is not incorporated in the resin (crosslinked) structure. Since the variation in the distance between the functional groups is extremely smaller than that of the functional group-containing monomer copolymer, the distance between the reaction points (crosslinking points) becomes constant and a uniform resin (crosslinking) structure is formed.

Next, in the case of a polymer having hydroxyl groups at both terminals and at least two hydroxyl groups at at least one terminal, it has hydroxyl groups at both terminals, but only at the terminals. As compared with a polymer having only one hydroxyl group, the crosslink density is increased, so that the physical strength of the crosslinked body can be improved, and due to the synergistic effect of the terminal OH group,
The advantage that the reactivity of the terminal OH group can be improved is recognized.

It has a hydroxyl group at both ends, and
In the case of using a polymer having at least two hydroxyl groups at at least one terminal, in the case of a thermosetting resin, it is necessary and expensive to cure a polymer having only one hydroxyl group at the terminal. It is not necessary to add a functional NCO compound or a trifunctional or higher functional polyol having poor handleability. Polymers having hydroxyl groups at both ends and at least two hydroxyl groups at at least one end are various resins such as polyester resins, polyurethane resins and polycarbonate resins, various block polymers, paints, by utilizing the above advantages. Elastic wall material, waterproof film, adhesive, floor material, tackifier, adhesive, binder (magnetic recording medium, ink binder, casting binder, baked brick binder, graft material, microcapsule, glass fiber sizing, etc.) , Sealing material, urethane foam (hard, semi-hard, soft), urethane RIM, UV / E
B-curing resin, high solid coating, thermosetting elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coating agent, artificial marble resin, artificial marble impact resistance-imparting agent , Resin for ink,
Extremely useful as raw materials for films (laminate adhesives, protective films, etc.), laminated glass resins, reactive diluents, various molding materials, elastic fibers, artificial leather, synthetic leather, etc., as well as various resin additives and their raw materials. Useful for.

[0007]

In order to obtain such a polymer having a hydroxyl group at both ends and at least two hydroxyl groups at at least one end, conventionally,
The only option was to modify the end-functional polymer. For example, when synthesizing a polymer having two hydroxyl groups at the ends, a method using a reaction represented by the following chemical formula 1 can be considered.

[0008]

[Chemical 1]

However, this method requires extra reaction steps and purification steps, and the reaction does not proceed 100%, so that the number of terminal functional groups is not improved as expected. As a result, there is a problem that the terminal functional characteristics cannot be sufficiently exhibited, which is not suitable for practical use. Thus, a method for industrially producing a polymer having hydroxyl groups at both ends has not been established. Therefore, there is a demand for the development of a reaction system capable of reliably and controlled introduction of a controlled number of OH groups at the terminal of the polymer and omitting or simplifying the purification step.

Various resins such as polyester resin, polyurethane resin and polycarbonate resin, various block polymers, paints, elastic wall materials, waterproof membranes, adhesives, floor materials, tackifiers, adhesives, binders (magnetic recording media , Ink binder, casting binder, baked brick binder, graft material, microcapsule, glass fiber sizing, etc.), sealing material, urethane foam (hard, semi-hard, soft), urethane RIM, UV / EB curing resin, high solid paint, Thermosetting elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coat agent, artificial marble resin, artificial marble impact resistance-imparting agent, ink resin, film (laminate Adhesives, protective films, etc.), resins for laminated glass, reactive diluents As a hydroxyl group-containing polymer used for various molding materials, elastic fibers, raw materials such as artificial leather and synthetic leather, and various resin additives and their raw materials, vinyl-based monomers having a hydroxyl group in the side chain. Examples of the copolymer include a polyether having a hydroxyl group at the terminal, polyester, polybutadiene, and polycarbonate. First, a copolymer of a vinyl monomer having a hydroxyl group in a side chain is a monomer having a hydroxyl group. , It is made by random radical polymerization with a monomer that does not have a hydroxyl group, so it is difficult to suppress the by-product of a copolymer that does not have a hydroxyl group, and if you try to avoid this, you increase the hydroxyl group content in the copolymer. It was necessary, and there were variations in the number of hydroxyl groups in one molecule. Therefore, when reacted with a polyfunctional compound having reactivity with a hydroxyl group, an unreacted copolymer remains, there is a large variation in the distance between reaction points, and a play not directly involved in the crosslinked structure after the reaction. A polymer which has sufficient elongation (bendability is good) and is also tough cannot be obtained because of the formation of chain portions and the remaining hydroxyl groups that do not participate in the reaction. On the other hand, polyethers having a hydroxyl group at the end, polyesters, polybutadiene, etc., have a hydroxyl group at the polymer end, so there are few defects such as copolymers of vinyl monomers having a hydroxyl group in the side chain, but polyethers. In the case of, the main chain has an ether bond, in the case of polyester, it has an ester bond in the main chain, and in the case of polybutadiene, it has poor weather resistance and water resistance due to the unsaturated double bond in the main chain. It has drawbacks. As mentioned above, at present, various resins such as polyester resin, polyurethane resin, polycarbonate resin, various block polymers, paints, elastic wall materials,
Waterproof film, adhesive, floor material, tackifier, adhesive, binder (magnetic recording medium, ink binder, casting binder, baked brick binder, graft material, microcapsule, glass fiber sizing, etc.), sealing material, Urethane foam (hard, semi-hard, soft), urethane RIM, UV / EB curing resin, high solid paint,
Thermosetting elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coat agent, artificial marble resin, artificial marble impact resistance-imparting agent, ink resin, film (laminate Adhesives, protective films, etc.), laminated glass resins, reactive diluents, various molding materials, elastic fibers, artificial leather, synthetic leather, etc., as well as various resin additives and hydroxyl groups used as raw materials, etc. There is no polymer which has all the required performances such as toughness, elongation (bending workability), weather resistance and water resistance.

In view of the above circumstances, the present invention provides a wide range of vinyl-based monomers including polar vinyl-based monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester at both ends. Method of easily and inexpensively and efficiently obtaining a polymer having a hydroxyl group and having at least two hydroxyl groups at at least one terminal, toughness, weather resistance and water resistance including the polymer It is an object of the present invention to provide a composition having a good composition, and a polymer derived from the composition.

[0012]

In order to solve the above-mentioned problems, a method for producing a polymer according to the present invention is directed to the polymerization of a vinyl monomer (a) with an alcohol (in which a polyfunctional alcohol is essential). b) in the presence of an initiator system (c) which essentially requires hydrogen peroxide, wherein components other than the above three components (a), (b) and (c) are placed in the reactor. It is characterized in that it does not substantially contain.

Here, the polymer obtained by the above-mentioned production method of the present invention is a polymer having a hydroxyl group at both ends and at least two hydroxyl groups at at least one end (hereinafter referred to as "polymer"). The coalescence may be referred to as "polymer A"). The composition according to the present invention comprises a polymer A,
The compound (d) having two or more functional groups capable of reacting with a hydroxyl group in one molecule is contained as an essential component.

The polymer having a polymerizable unsaturated group according to the present invention comprises the polymer A having two kinds of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group, in one molecule. It is obtained by reacting with the compound (h) which is also contained. The polymer having a polymerizable unsaturated group has a polymerizable unsaturated group at both ends and at least two polymerizable unsaturated groups at at least one end (hereinafter, this polymer will be referred to as "polymer Sometimes referred to as "B").

The polymer having a carboxyl group according to the present invention is a compound (i) having the polymer A having two reactive groups of a functional group capable of reacting with a hydroxyl group and a carboxyl group in one molecule. And / or is obtained by reacting with an acid anhydride. The polymer having a carboxyl group has a carboxyl group at both ends and at least two carboxyl groups at at least one end (hereinafter, this polymer may be referred to as "polymer C").

The polyurethane according to the present invention is obtained by reacting a polyol component (j) essentially containing the polymer A with a polyfunctional isocyanate compound (e) having two or more isocyanate groups in one molecule. Polyurethane (hereinafter, simply referred to as "polyurethane of the present invention"). The polyester according to the present invention is a polyester obtained by reacting a polyol component (j) essentially containing the polymer A with a compound (g) having two or more carboxyl groups in one molecule (hereinafter, referred to as It is simply referred to as "polyester of this invention").

The block polymer according to the present invention is characterized by containing the polymer A as an essential component. Hereinafter, first, a method for producing a polymer according to the present invention will be described. The vinyl-based monomer (a) used in the present invention is not particularly limited as long as it is a conventionally known vinyl-based monomer. For example, (meth) acrylic acid; methyl (meth) acrylate, (meth) Ethyl acrylate,
Butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylic acid alkyl esters such as n-octyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate; (meth) acrylic acid aryl esters such as benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate,
(meth) acrylic acid substituent-containing alkyl esters such as γ- (methacryloyloxypropyl) trimethoxysilane; methoxyethyl (meth) acrylate, (meth)
(Meth) such as ethylene oxide adduct of acrylic acid
Acrylic acid derivatives; perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate,
Perfluoroalkyl esters of (meth) acrylic acid such as perfluorobutyl (meth) acrylate and perfluorooctyl (meth) acrylate; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, Aromatic vinyl monomers such as styrene, α-methylstyrene, methylstyrene, chlorostyrene, styrenesulfonic acid and its sodium salt; perfluoromethyl (meth) acrylate, ( (Meth) trifluoromethyl methyl acrylate,
2-trifluoromethylethyl (meth) acrylate,
(Meth) acrylic acid diperfluoromethylmethyl, (meth) acrylic acid 2-perfluoroethylethyl, (meth) acrylic acid 2-perfluoromethyl-2-perfluoroethylmethyl, (meth) acrylic acid triperfluoromethyl Methyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) acrylic acid 2 -Fluorine-containing vinyl monomers such as perfluorohexadecylethyl, perfluoroethylene, perfluoropropylene, and vinylidene fluoride; trialkyloxysilyl group-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane Kinds; γ- (methacryloyloxypro Silicon) vinyl-containing monomers such as trimethoxysilane; maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile. , Vinyl monomers containing nitrile group such as methacrylonitrile; vinyl monomers containing amide group such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate Vinyl esters such as ethylene,
Examples include alkenes such as propylene; dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. These may be used alone or in combination of two or more. May be.

As seen above, the vinyl monomer (a) used in the present invention may have a functional group such as a hydroxyl group, a carboxyl group or an amino group in the molecule. Especially when a relatively high crosslinking density is required, it is rather preferable to use a small amount of a vinyl-based monomer having a functional group in combination, for example, for coating applications. The amount of the vinyl-based monomer having a functional group is not particularly limited. For example, in the case of a vinyl-based monomer having a hydroxyl group, the hydroxyl group is added to the total amount of the vinyl-based monomer (a) used. The vinyl-based monomer has preferably 1 to 50% by weight, and more preferably 5 to 30% by weight.

It is preferable that the vinyl monomer having a carboxyl group is 0.5 to 25% by weight.
More preferably, it is 10% by weight. As described above, the vinyl-based monomer (a) is not particularly limited as long as it is a conventionally known vinyl-based monomer. It is preferable that the main component is a (meth) acrylic acid-based monomer. In this case, it is preferable that the (meth) acrylic acid ester-based monomer is contained in an amount of 40% by weight or more based on the entire vinyl-based monomer (a).

When gloss or hardness of the coating film is required, it is preferable to use an aromatic vinyl monomer.
In this case, it is preferable that the aromatic vinyl-based monomer is contained in an amount of 40% by weight or more based on the entire vinyl-based monomer (a). Further, when water repellency, oil repellency, stain resistance and the like are required, it is preferable to use a fluorine-containing vinyl monomer. In this case, it is preferable that the fluorine-containing vinyl monomer is contained in an amount of 10% by weight or more based on the entire vinyl monomer (a).

When adhesion with an inorganic material and stain resistance are required, it is preferable to use a silicon-containing vinyl monomer. In this case, it is preferable that the silicon-containing vinyl-based monomer is contained in an amount of 10% by weight or more based on the entire vinyl-based monomer (a). In the present invention, the polyfunctional alcohol used in the alcohols (b) in which the polyfunctional alcohol is essential is not particularly limited as long as it is a compound having at least two hydroxyl groups in one molecule. Glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol , Alkylene glycols such as 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, and 1,6-hexanediol; hydroquinone diethylol Ether; ethylene glycol such as diethylene glycol and triethylene glycol Conductor; sorbitol, cyclohexanediol, aliphatic such xylylenediol polyfunctional alcohols; glycerol and monoacetin, monolaurin, monoolein,
Glycerol 1-substituted derivatives such as glycerol fatty acid esters such as monopalmitin and monostearin and glycerol monoallyl ethers such as glycerol monoallyl ether, thymyl alcohol, glycerol monomethyl ether and batyl alcohol; trimethylolpropane and its monosubstituted derivatives; pentaerythritol and penta Pentaerythritol 2-substituted derivatives such as erythritol 2 oleate and pentaerythritol 2 stearate; sorbitan fatty acid ester;
Erythritol, threose, ribose, arabinose, xylose, lyxose, allose, altose,
Examples include monosaccharides such as glucose, mannose, gulose, idose, galactose, talose, fructose, apiose, rhamnose, psicose, sorbose, tagitose, ribulose and xylulose, and disaccharides such as sucrose, maltose and lactose. Among these, ethylene glycol, 1,4-butanediol, trimethylolpropane, glycerol, pentaerythritol and sorbitol are preferably used.

The polyfunctional alcohol is not limited to those containing only carbon, hydrogen and oxygen as constituent elements. For example, it may contain a nitrogen element or a sulfur element in addition to the above three elements. The nitrogen element-containing polyfunctional alcohol that can be used is not particularly limited, but examples thereof include amine-based polyfunctional alcohols such as phenyldiethanolamine, triethanolamine, triisopropanolamine, diethanolamine, diisopropanolamine, and trishydroxymethylaminomethane; Examples thereof include trishydroxycyanuric acid.

As the sulfur element-containing polyfunctional alcohol, use should be made of polyfunctional alcohols having various bonds containing elemental sulfur such as C═S bond, C—S—C bond, SO ₂ bond and SO ₃ bond. You can However, in the present invention, a polyfunctional alcohol having an SH bond or an S _n bond (n ≧ 2) cannot be used. The reason is as follows. SH bond and S _n bond (n ≧ 2)
Has a high reactivity to radicals, and therefore has a large chain transfer constant, and the reactions shown in Formulas 2 and 3 below easily occur. Therefore, it is very difficult to introduce hydroxyl groups at both ends of the polymer and at least two hydroxyl groups at at least one end.

[0024]

[Chemical 2]

[0025]

[Chemical 3]

Furthermore, the SH bond and the S _n bond are easily oxidized by hydrogen peroxide, and the hydrogen peroxide is wasted as in the reactions shown in the following chemical formulas 4 and 5, resulting in polymerization. A decrease in the rate and an increase in the molecular weight occur.

[0027]

[Chemical 4]

[0028]

[Chemical 5]

The sulfur element-containing polyfunctional alcohol that can be used is not particularly limited as long as it has neither SH bond nor S _n bond (n ≧ 2). For example, thiodiethylene glycol, ethylene bis-2 −
Hydroxyethyl sulfide, bishydroxyethyl sulfone, N, N-bis (2-hydroxyethyl) taurine and metal salts thereof, laurylthiopropionic acid thiodiethanolamine salt, ethylene oxide adduct of thioethylene glycol, bis (2-hydroxyethyl) bisphenol -S, bis (2-hydroxyethyl) tetrabromobisphenol-S, bis (2-hydroxyethyl)
Tetramethylbisphenol-S, bis (2-hydroxyethyl) diphenylbisphenol-S, bis (2-
Hydroxyethyl) thiodiphenol and the like can be mentioned.

The polyfunctional alcohols may be used alone or in combination of two or more. By appropriately selecting the type of polyfunctional alcohol, the number of terminal functional groups can be easily controlled. As a result, without using a vinyl-based monomer having a functional group in combination, the toughness, the weather resistance, and the water resistance, which are the characteristics of the terminal functional polymer, are not impaired, and the crosslinking density with a balanced performance of the crosslinked body is obtained. It becomes possible to obtain.

In order to adjust the solubility of the polyfunctional alcohol and the viscosity of the polymerization system, it is possible to add a monofunctional alcohol having only one hydroxyl group in the molecule. However, in this case, the monofunctional alcohol acts as a chain transfer agent in the polymerization reaction, and it becomes impossible to introduce a functional group into the terminal. It is preferable that the weight fraction in b) is less than 50%.

The polyfunctional alcohol can be used in the reaction system as an aqueous solution. In this case, the concentration of the aqueous solution is not particularly limited, but the concentration of the polyfunctional alcohol aqueous solution is preferably 50% by weight or more in view of controlling the molecular weight of the polymer and controlling the reaction temperature. Examples of the initiator system (c) containing hydrogen peroxide as an essential component used in the present invention include a case where a compound (k) capable of promoting polymerization by combination with hydrogen peroxide is used in combination with hydrogen peroxide, An example is when hydrogen peroxide is used alone. Hydrogen peroxide can be used as an industrially available aqueous solution, and the concentration thereof is not particularly limited. Examples of the compound (k) include a hydrogen peroxide decomposition catalyst, a reducing compound that performs a redox reaction with hydrogen peroxide, a surfactant, and the like. That is, the initiator system (c) that essentially requires hydrogen peroxide is hydrogen peroxide alone, or hydrogen peroxide is an essential component and is composed of a hydrogen peroxide decomposition catalyst, a reducing compound and a surfactant. It is a mixture containing one or more compounds selected from the group consisting of and capable of promoting polymerization. Hereinafter, the compound (k) capable of promoting the polymerization by combining with hydrogen peroxide will be specifically described.

The hydrogen peroxide decomposition catalyst used in the present invention is not particularly limited, but examples thereof include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, sulfuric acid, Nitric acid, perchloric acid,
Inorganic acids such as hydrobromic acid and metal salts thereof; benzenesulfonic acid, alkylbenzenesulfonic acids such as p-toluenesulfonic acid and metal salts thereof; carboxyne such as formic acid, acetic acid, propionic acid, lacic acid, isolacic acid and benzoic acid. Acids and metal salts and esters thereof; heterocyclic amines such as pyridine, indole and its derivatives, imidazole and its derivatives, carbazole and its derivatives, and the like.

Examples of the compound that undergoes redox reaction with hydrogen peroxide used in the present invention include organometallic compounds such as ferrocene; inorganic metal compounds capable of generating metal ions such as iron, copper, nickel and cobalt in water. Inorganic compounds such as boron fluoride ether adduct, potassium permanganate, perchloric acid; sulfur dioxide, sulfite, sulfuric acid mono- or di-alkyl ester, sulfuric acid mono- or di-allyl ester, bisulfite Sulfur-containing inorganic compounds such as salts, thiosulfates, sulfoxylates, benzenesulfinic acid and its substitutes, and homologs of cyclic sulfinic acids such as paratoluenesulfinic acid; octyl mercaptan,
Mercyl compounds such as decyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercaptopropionic acid, thioglycolic acid, thiopropionic acid, α-thiopropionic acid sodium sulfopropyl ester, α-thiopropionic acid sodium sulfoethyl ester, hydrazine, β -Hydroxyethylhydrazine,
Nitrogen-containing compounds such as hydroxylamine, formaldehyde, acetaldehyde, propionaldehyde, n
-Aldehydes such as butyraldehyde, isobutyraldehyde, isovalerianaldehyde, and ascorbic acid.

Examples of the surfactant used in the present invention include triethylbenzylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride and N-laurylpyridinium chloride. , Trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, trimethylphenylammonium bromide,
Tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogensulfate, N-benzylpicolinium chloride, tetramethylammonium iodide, tetra-n-butylammonium iodide , Quaternary ammonium salts such as N-lauryl-4-picolinium chloride and N-lauryl-4-picolinium chloride; phosphonium salts such as tetrabutylphosphonium chloride; sulfonium salts such as trimethylsulfonium iodide; ; Or p-
Alkylbenzene sulfonic acids such as toluene sulfonic acid and dodecyl benzene sulfonic acid, and metal salts thereof; or polyoxyethylene-polypropylene oxide block copolymers; polyoxyethylene-based surfactants such as polyoxyethylene sulfates; lauryl alcohol, Higher alcohols such as stearyl alcohol; and sulfuric acid esters of these higher alcohols and metal salts of the sulfuric acid esters; higher fatty acids such as lauric acid and stearic acid and metal salts of these higher fatty acids, and the like. They may be used, or a plurality of types may be used.

Among the above-mentioned surfactants, the alkylbenzene sulfonic acid, onium salt, and phosphorus-containing surfactants are preferable because they have the effect of accelerating the decomposition of hydrogen peroxide in addition to the surfactant activity. In particular, dodecylbenzene sulfonic acid is more preferable. Further, a surfactant having a hydroxyl group at both ends itself, such as a polyoxyethylene-polypropylene oxide block copolymer, is incorporated into the cross-linked structure, so that the toughness, weather resistance and water resistance of the cross-linked product are improved. Since no adverse effect is given, purification and removal are not required, which is preferable.

In the production method of the present invention, during the reaction, the vinyl-based monomer (a), the alcohols (b) in which the polyfunctional alcohol is essential, and the initiator system in which hydrogen peroxide is essential in the reactor. Substantially do not use anything other than (c). Specifically, the components other than the vinyl-based monomer (a), the alcohols (b) that require a polyfunctional alcohol, and the initiator system (c) that requires hydrogen peroxide are 10% by weight of the whole.
It should be below. Then, (a), (b),
The components other than (c) are preferably 5% by weight or less, and most preferably, the components other than (a), (b) and (c) are not contained at all.

The polymerization vessel (reactor for carrying out the polymerization reaction) used in the present invention may be a batch type such as a general tank type reactor or a kneader, or a piston flow tube type type, Depending on the viscosity of the polymer, a continuous type extruder such as a twin-screw extruder or a continuous kneader may be used. Also, it can be used in a semi-batch type reactor without any problem, but the concentration ratio of each additive in the reactor can be easily controlled by adding each additive in the middle of the tube, and that the residence time is constant From the viewpoint of good productivity and the like, it is preferable to use a tubular reactor, an extruder or a continuous kneader. Regarding the proper use of a tubular reactor, an extruder and a continuous kneader, it is preferable to use a tubular reactor for a low viscosity after polymerization and an extruder or a continuous kneader for a relatively high viscosity.

However, for the liquid contact part of these devices, a material suitable for hydrogen peroxide should be selected.
US316, 304L, Teflon, aluminum, glass, etc. can be mentioned. Among these, Teflon, aluminum and glass are preferable, and Teflon and glass are most preferable. The structure of the tubular reactor is not particularly limited, and is a conventionally known tubular reaction such as a single-tube type, a multi-tube type, or a mixer with no moving parts (such as Noritake Company or Sumitomo Sulzer). Although any reactor can be used, it is preferable to use a tubular reactor using a mixer having no moving parts from the viewpoints of mixing and heat exchange efficiency. Similarly, for extruders and continuous kneaders,
Any conventionally known extruder such as a single-screw type or a twin-screw type can be used, but in terms of mixing, heat exchange efficiency, etc.,
It is preferable to use a biaxial extruder or a continuous kneader.

In the present invention, the reaction can be carried out at atmospheric pressure, but it can also be carried out under pressure in an autoclave or an extruder. The polymerization temperature in the production method of the present invention is also not particularly limited, and there is no problem as long as it is from room temperature to 200 ° C at which ordinary radical polymerization is carried out. In the present invention, since the polyfunctional alcohol itself has two or more hydroxyl groups in the molecule, it is incorporated into the crosslinked structure, so that the toughness of the crosslinked product is
The polyfunctional alcohol may be contained in the polymer as long as the adverse effects on the weather resistance and water resistance do not appear, and the purification process may be simplified in some cases.

The molecular weight of the polymer A produced by the present invention is not particularly limited, but the number average molecular weight of the polymer A is 500 to 100,000 in order to exert the characteristics resulting from having a reactive hydroxyl group at the terminal. Is preferable, and the number average molecular weight is more preferably 1,000 to 50,000. The average number of terminal hydroxyl groups (Fn (OH)) of the polymer A produced by the present invention is ideally 4.0 when the polyfunctional alcohol is ethylene glycol, but is 3.6 to 4 If it is 0.0, it is possible to exhibit substantially the same physical properties as the ideal one, which is very preferable. If it is at least 3.0, physical properties close to ideal can be exhibited. For this reason, the average number of terminal hydroxyl groups (Fn
(OH)) may be 3.0 or more. However, even if the average number of terminal hydroxyl groups of the polymer A is less than 3, if it is 2 or more, when used as various resin raw materials (crosslinking agent etc.) such as polyester resin and polyurethane resin, the physical properties of the material are not impaired. Since there are no reactants and all the polymers are surely incorporated into the resin cross-linked structure, it is possible to exhibit the characteristics attributed to having a reactive hydroxyl group at the terminal.

The polymer A obtained by the production method of the present invention has a terminal hydroxyl group which can be easily polymerized with a polymerizable unsaturated group such as an amino group, a carboxyl group or a vinyl group by utilizing a conventionally known organic reaction. , Epoxy group, silanol group, alkoxysilyl group, hydrosilyl group, mercapto group, oxazoline group, lactone group, azlactone group, ethynyl group, maleimide group, formyl group, bromine, chlorine, etc. it can.

Next, the composition according to the present invention will be described. As described above, the composition of the present invention contains, as an essential component, the polymer A and the compound (d) having two or more functional groups capable of reacting with a hydroxyl group in one molecule. Polymer A may use only 1 type and may use 2 or more types together. The weight ratio of the polymer A and the compound (d) (polymer A / compound (d)) contained in this composition is not particularly limited, but is 99.99 / 0.
It is preferably 01 to 40/60, and 99.9 /
It is more preferably 0.1 to 60/40.

The composition of the present invention comprises, in addition to polymer A,
It may contain a conventionally known low molecular weight compound having a hydroxyl group and a conventionally known polymer having a hydroxyl group (polymer polyol, acrylic polyol, polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyolefin polyol, etc.).

The compound (d) having two or more functional groups capable of reacting with the hydroxyl group in one molecule is not particularly limited, but for example, a compound (e) having two or more isocyanate groups in one molecule (e). ), An aminoplast resin (f) such as a methylolated melamine and its alkyl ether compound or a low condensation product thereof, a compound (g) having two or more carboxyl groups in one molecule such as a polyfunctional carboxylic acid and its halide. Is mentioned.

The compound (e) having two or more isocyanate groups in one molecule is a so-called polyfunctional isocyanate compound. As the polyfunctional isocyanate compound (e), any conventionally known compounds can be used. For example, tolylene diisocyanate (“TD
I "), 4,4'-diphenylmethane diisocyanate (also referred to as" MDI "), hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Isocyanate compounds such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate; Burette polyisocyanate compounds such as Sumidule N (Sumitomo Bayer Urethane Co.); Desmodur IL, HL (Bayer AG) , Coronate EH (Japan Polyurethane Industry Co., Ltd.)
Polyisocyanate compounds having an isocyanurate ring such as SUMIJURE L (manufactured by Sumitomo Bayer Urethane Co., Ltd.) and adduct polyisocyanate compounds such as Coronate HL (manufactured by Nippon Polyurethane Co.). be able to. These may be used alone or in combination of two or more. In addition, blocked isocyanate may be used.

In order to take advantage of the excellent weather resistance of the composition containing the polymer A and the polyfunctional isocyanate compound (e), the polyfunctional isocyanate compound (e) may be, for example, hexamethylene diisocyanate, Hydrogenated diphenylmethane diisocyanate, Sumidule N
It is preferable to use an isocyanate compound having no aromatic ring such as (Sumitomo Bayer Urethane Co., Ltd.).

Polymer A and polyfunctional isocyanate compound (e) having two or more isocyanate groups in one molecule
The compounding ratio with is not particularly limited, but for example, the ratio (NCO / OH (molar ratio)) of the isocyanate group of the compound (e) to the hydroxyl group of the polymer A is 0.5 to 1 Preferably 0.5, 0.8
More preferably, it is 1.2. However, when this composition is used in applications where excellent weather resistance is required,
It may be used in a molar ratio up to about NCO / OH = 3.0.

In order to accelerate the urethanization reaction between the polymer A, which is a component in the composition of the present invention, and the polyfunctional isocyanate compound (e), an organotin compound or a tertiary compound may be added, if necessary. The use of known catalysts such as amines is free. The aminoplast resin (f) used in the composition of the present invention is not particularly limited, but for example, a reaction product (methylol compound) of a triazine ring-containing compound represented by the following general formula 6 and formaldehyde, Low condensation product of triazine ring-containing compound and formaldehyde, derivatives thereof, and urea resin, and
Examples thereof include a reaction product (methylol compound) of a urea resin and formaldehyde, a low condensation product of a urea resin and formaldehyde, and derivatives thereof.

[0050]

[Chemical 6]

The triazine ring-containing compound represented by the above general formula 6 is not particularly limited, and examples thereof include melamine, benzoguanamine, cyclohexanecarboguanamine, methylguanamine, vinylguanamine and the like. These may be used alone,
You may use 2 or more types together. The reaction product of the triazine ring-containing compound and formaldehyde or a derivative thereof is not particularly limited, but examples thereof include hexamethoxymethylmelamine and tetramethoxymethylbenzoguanamine. As the low-condensation compound or a derivative of said triazine ring-containing compound and formaldehyde is not particularly limited, for example, the triazine ring-containing _{compound, -NH-CH 2 -O-CH} 2 -NH-
Binding and / or low condensate products and alkyl-etherified formaldehyde resin was several bonded via -NH-CH ₂ -NH- bond [Cymel (manufactured by Mitsui Cyanamid Co.
Manufactured)] and the like. These aminoplast resins (f) may be used alone or in combination of two or more.

Aminoplast resin (f), examples of which were given above
The ratio of the triazine ring-containing compound and formaldehyde used in synthesizing the compound varies depending on the application used, but the molar ratio of the triazine ring-containing compound and formaldehyde (triazine ring-containing compound / formaldehyde) is 1 to It is preferably in the range of 6,
The range of 1.5 to 4 is more preferable.

Next, in the composition of the present invention containing the polymer A and the aminoplast resin (f) as the compound (d) as essential components, the ratio of the polymer A to the aminoplast resin (f) ( The weight ratio) is preferably 95: 5 to 50:50, more preferably 80:20 to 60:40. Polymer A and aminoplast resin (f) as essential components,
In the composition of the present invention, it is free to use conventionally known catalysts such as paratoluenesulfonic acid and benzenesulfonic acid for promoting the reaction.

The ratio (weight ratio) of the polymer A and the amino compound in the composition essentially containing the polymer A and the aminoplast resin (f) is preferably 95: 5 to 50:50, and 80:20 to 60. : 40 is more preferable. The compound (g) having two or more carboxyl groups in one molecule used in the composition of the present invention is not particularly limited, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. , Phthalic acid, phthalic anhydride, terephthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, diphenic acid, naphthalenedicarboxylic acid, etc. Examples of the polyfunctional carboxylic acid or its anhydride, halides thereof, polymers having a plurality of carboxyl groups, and the like. As the compound (g), only one type may be used, or two or more types may be used in combination. The molar ratio of the compound (g) to the hydroxyl group in the polymer A (compound (g) / hydroxyl group in the polymer A) is 1 to 3.
Is preferable, and 1-2 is more preferable.

When the composition of the present invention is used as a coating composition, the hardness of the coating film is required, so that a certain degree of crosslink density is required. Therefore, as the polymer A used for coating purposes, those having a hydroxyl value of about 20 to 450 are preferable. That is, when the monomer having a hydroxyl group is not copolymerized, the number average molecular weight of the polymer A is 50
About 0 to 12000 is preferable. However, even those having a number average molecular weight of more than 12,000 can be used by copolymerizing a monomer having a hydroxyl group. Also,
When the composition of the present invention is used as a coating composition, the Tg (glass transition temperature) of the polymer A is from -30 ° C to
100 degreeC is preferable and -10 degreeC-60 degreeC is more preferable. The polymer A having a desired Tg can be synthesized by adjusting the type and proportion of the vinyl-based monomer (b) used. When the aminoplast resin (f) is used, it is preferable to copolymerize an acid group-containing vinyl monomer as an internal acid catalyst.

When the composition of the present invention is used as a coating composition, in addition to the polymer A, a conventionally known low molecular weight compound having a hydroxyl group and a conventionally known polymer having a hydroxyl group (polymer polyol, acrylic polyol, polyether) are used. (Polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyolefin polyol, etc.), a conventionally known coating resin, etc. may be contained.

When the composition of the present invention is used as a pressure-sensitive adhesive composition, the Tg of the polymer A is preferably −20 ° C. or lower, and its molecular weight (weight average molecular weight) is
Is preferably 1000 to 1,000,000.
A low molecular weight polymer A having a weight average molecular weight of about 1000 to 10000 is combined with a bifunctional isocyanate compound or the like to be applied to a base material and then chain-extended,
When used as an adhesive, compared to the case where a conventional polymer obtained by copolymerizing a vinyl-based monomer having a functional group is used (usually, one having a weight average molecular weight of 100,000 or more is used) Since the pressure-sensitive adhesive composition has a low viscosity, the amount of the solvent used can be reduced, workability can be improved, and other effects not obtained by the conventional pressure-sensitive adhesive composition can be obtained.
Further, in order to further improve the adhesiveness with the base material, it is preferable to copolymerize the acid group-containing monomer.

When the composition of the present invention is used as a composition for pressure-sensitive adhesives, conventionally known additives such as tackifiers, plasticizers, fillers and antioxidants may be added to the composition, if necessary. Agents may be included. The tackifier that can be used is not particularly limited, for example, rosin-based,
Examples include rosin ester resins, polyterpene resins, chroman-indene resins, petroleum resins and terpene phenol resins. The plasticizer is not particularly limited, but examples thereof include liquid polybutene, mineral oil, lanolin, liquid polyisoprene, and liquid polyacrylate. The filler is not particularly limited, and examples thereof include zinc white, titanium white, calcium carbonate, clay and various pigments. The anti-aging agent is not particularly limited, but examples thereof include rubber-based antioxidants (phenol-based and amine-based) and metal dithiocarbamates. Each of the tackifiers, plasticizers, fillers and antioxidants listed above may be used alone or in combination of two or more.

When the composition of the present invention is used as an adhesive composition, the molecular weight (weight average molecular weight) of the polymer A is
It is preferably 1000 to 1,000,000. By combining this polymer A with a conventionally known isocyanate compound or the like, it can be used as a one-component or two-component adhesive. When the composition of the present invention is used as an adhesive composition, in the composition, if necessary, conventionally known polyols (low molecular weight polyols, high molecular weight polyols), tackifiers, Additives such as coupling agents, thixotropic agents, inorganic fillers and stabilizers may be included. The polyols that can be used are not particularly limited, and examples thereof include low molecular weight polyols such as ethylene glycol (also referred to as EG), diethylene glycol (also referred to as DEG), dipropylene glycol (also referred to as DPG), and 1,4-butanediol ( 1,4-BD), 1,6-hexanediol (also called 1,6-HD), neopentyl glycol (also called NPG), trimethylolpropane (TMP)
Also referred to as “polyether glycol (polyethylene glycol (PE
G), polypropylene glycol (also called PPG), ethylene oxide / propylene oxide copolymer (also called EO / PO copolymer), polytetramethylene glycol (also called PTMEG)], polyester polyol, castor oil, liquid polybutadiene. , Epoxy resin, polycarbonate diol, acrylic polyol and the like. The tackifier is not particularly limited, for example, terpene resin, phenol resin,
Examples thereof include terpene-phenol resin, rosin resin and xylene resin. The coupling agent is not particularly limited, but examples thereof include a silane coupling agent and a titanium coupling agent. The inorganic filler is not particularly limited, but examples thereof include carbon black, titanium white, calcium carbonate, and clay. The thixotropic agent is not particularly limited, and examples thereof include Aerosil and Disparlon. The stabilizer is not particularly limited, and examples thereof include an ultraviolet absorber, an antioxidant, a heat resistance stabilizer, and a hydrolysis resistance stabilizer. The above-mentioned polyols, tackifiers,
Coupling agents, thixotropic agents, inorganic fillers and stabilizers
For each, only one kind may be used, or two or more kinds may be used in combination.

The application of the above-mentioned adhesive is not particularly limited, but for example, an adhesive for food packaging, an adhesive for shoes / footwear, an adhesive for decorative paper, an adhesive for wood, a structural adhesive (automobile,
Examples include septic tanks, housing) adhesives, magnetic tape binders, fiber processing binders, fiber treatment agents, and the like. When the composition of the present invention is used as a urethane foam composition,
In the composition, if necessary, conventionally known polyols (low molecular weight polyols, high molecular weight polyols, etc. other than the polymer A obtained by the production method of the present invention), polyisocyanates (for example, TDI, MDI
Etc.), catalyst (for example, amine-based, tin-based, etc.), water, surfactant (for example, silicon-based, nonionic, ionic-based, etc.), additive (for example, flame retardant, antimicrobial agent, colorant,
A filler, a stabilizer, etc.), a foaming aid (for example, a halogenated hydrocarbon, etc.) and the like may be contained.

When the composition of the present invention is used as a sealant composition, the molecular weight of the polymer A (weight average molecular weight)
Is preferably 1000 to 1,000,000.
When the composition of the present invention is used as a sealant composition, in the composition, if necessary, conventionally known polyols (high molecular weight polyols other than the polymer A, etc.), polyisocyanates (for example, TDI, MDI
Etc.), catalysts (eg amine-based, tin-based, lead-based etc.), inorganic fillers (eg calcium carbonate, talc, clay, silica, carbon black, titanium white etc.), plasticizers [eg dioctyl phthalate ( DOP), di-i-decyl phthalate (also referred to as DIDP), dioctyl adipate (also referred to as DOA), etc.], anti-drip agent (for example, colloidal silica, hydrogenated castor oil, organic bentonite, surface-treated calcium carbonate) Etc.), antiaging agents (eg hindered phenols, benzotriazole,
Hindered amines, etc.), a foaming inhibitor (eg, dehydrating agent, carbon dioxide absorbent, etc.) and the like may be contained.

When a polymer obtained by converting the hydroxyl group of the polymer A obtained by the production method of the present invention into a hydroxysilyl group, an alkoxysilyl group, or a mercapto group is used as an essential component of the sealant composition, The sealing material composition becomes a sealing material composition having a crosslinking system different from urethane. Next, the polymer B having a polymerizable unsaturated group according to the present invention will be described.

When synthesizing this polymer B, a compound having two kinds of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group, to be reacted with the polymer A in one molecule ( The h) is not particularly limited, and examples thereof include a vinyl-based monomer having an isocyanate group, a carboxyl group, a methylolated triazine ring, and the like. More specifically, for example, methacryloyloxyethyl isocyanate, methacryloyl isocyanate,
Isopropenyl dimethylbenzyl isocyanate, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, succinic acid, succinic anhydride and halides of these carboxyl groups, and vinylguanamine methylol compounds Etc.

At the time of this reaction, it is free to use a solvent or a conventionally known catalyst. An example of this catalyst is
When the functional group of the compound (h) is an isocyanate group, a tertiary amine such as triethylamine, a tin compound such as dibutyltin dilaurate, or the like is used when the functional group is a carboxyl group or an acid anhydride group. Include amine compounds such as triethylamine and pyridine,
Inorganic acids such as sulfuric acid, and organic acid alkali metal salts such as sodium acetate, when the functional group is a methylolated triazine ring, sulfonic acids such as dodecylbenzene sulfonic acid and other weak acids, etc. Can be mentioned.

When the polymer B is used as an essential component of the composition, other components contained in the composition include, for example, a vinyl monomer having one polymerizable unsaturated group in one molecule. Can be mentioned. The vinyl-based monomer is not particularly limited, and conventionally known ones can be used without any problem. For example, those mentioned above as examples of the vinyl-based monomer (b) can be mentioned. This composition may contain a conventionally known polymerization initiator, if necessary. The energy source for initiating the polymerization is not particularly limited, but for example, light, EB, U
V, radiation, heat, etc. can be used.

Examples of the composition containing the polymer B and a vinyl monomer having one polymerizable unsaturated group in one molecule as essential components include a gel coat resin composition and an artificial marble described in detail below. Resin compositions for use. The gel coat resin composition may contain 2 or more molecules in one molecule, if necessary.
It may also contain a polyfunctional vinyl-based monomer having at least one polymerizable unsaturated group. The polyfunctional vinyl-based monomer is not particularly limited, but for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, propylene glycol di (meth) acrylate, methylene. Bisacrylamide, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, di Examples thereof include pentaerythritol hexa (meth) acrylate. These can be used alone or in combination of two or more.

The weight ratio of the polymer B and the vinyl monomer contained in the gel coat resin composition (polymer B / vinyl monomer) is not particularly limited, but is 10/90 to 60.
/ 40 is preferable, and 20/80 to 50/50 is more preferable. When this ratio is smaller than 10/90, the reaction shrinkage of the gel coat resin layer is too large, so that the shrinkage strain becomes large and it becomes difficult to obtain a good coat surface. Further, when the ratio is more than 60/40, the viscosity of the gel coat resin composition becomes too high, and the workability is likely to be extremely lowered.

To obtain the surface hardness of the gel coat layer,
The Tg of the polymer B and the Tg of the vinyl-based monomer used for this purpose are both preferably 20 ° C. or higher. Further, when it is necessary to increase the crosslink density in order to obtain the surface hardness, a vinyl-based monomer having a hydroxyl group is copolymerized with the polymer A, which is a precursor of the polymer B, or the above polyfunctional compound is used. It is preferable to use the vinyl-based monomer in a proportion of 50% by weight or less.

If necessary, a polymerization inhibitor such as hydroquinone, catechol, or 2,6-ditertiarybutylparacresol is added to the gel coat resin composition, and a radical polymerization initiator generally used, In particular, it is cured with an organic peroxide initiator or the like. When an organic peroxide initiator is used, various reducing metal salts such as cobalt naphthenate, nickel naphthenate and iron naphthenate, and curing accelerators such as reducing compounds such as amines and mercaptans are used together. You may.

If necessary, the gel coat resin composition may further include a dye, a plasticizer, an ultraviolet absorber, and the like, and conventionally known thixotropic agents such as silica, asbestos powder, hydrogenated castor oil, and fatty acid amide. Various additives such as a filler, a stabilizer, a defoaming agent, and a leveling agent can be added. The artificial marble resin composition may contain, if necessary, a polyfunctional vinyl-based monomer having two or more polymerizable unsaturated groups in one molecule, a filler, a curing agent, a thermoplastic polymer, or the like. Addition of additives etc. is free.

The polyfunctional vinyl-based monomer optionally added to the resin composition for artificial marble is not particularly limited, but ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene. Polyfunctional (meth) acrylates such as glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Examples include methylenebis (meth) acrylamide, divinylbenzene and the like. The addition amount of the polyfunctional vinyl-based monomer is not particularly limited, but the total amount of the polymer B, the vinyl-based monomer having one polymerizable unsaturated group in one molecule, and the polyfunctional vinyl-based monomer. Is preferably 40% by weight or less. This is because if the amount of the polyfunctional vinyl monomer added exceeds 40% by weight, the resulting artificial marble becomes hard and brittle, which is not desirable.

Fillers added as necessary to the artificial marble resin composition include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium carbonate, talc, clay, silica, quartz, alumina, zirconia,
Glass powder, glass fiber, marble, limestone, pyroxene,
Examples include natural crushed stones such as amphibole, sandstone, granite, and basalt, and crushed products of unsaturated polyester resin, synthetic resin such as thermosetting acrylic resin and melamine resin. The addition amount of the filler is not particularly limited, but is 100 to 100 with respect to the total amount of the polymer B, the vinyl-based monomer having one polymerizable unsaturated group in one molecule, and the polyfunctional vinyl-based monomer. 80
0% by weight is preferred. If the amount added is less than 100% by weight, the heat resistance and flame retardancy may be insufficient, and if it exceeds 800% by weight, polymer B contains a polymerizable unsaturated group in one molecule. The dispersibility of the filler in the vinyl-based monomer and the polyfunctional vinyl-based monomer having one becomes insufficient, or the fluidity during molding and curing is impaired, and uniform artificial marble cannot be obtained. Sometimes.

The hardener added to the artificial marble resin composition as required is not particularly limited, but examples thereof include benzoyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, and bis (4-t-butylcyclohexyl). ) Peroxydicarbonate, t-butyl peroxybenzoate, t-butyl peroxy octoate and the like can be mentioned. Among them, t-butyl peroxyoctoate and benzoyl peroxide, which are a medium / high temperature curing agent, which give a cured product having good transparency without cracks, are preferable for press molding. The medium / low temperature curing agent may be used alone or in combination with a curing accelerator together with an organic amine or a salt of a polyvalent metal.
t-butylcyclohexyl) peroxydicarbonate (Percadox PX-16, manufactured by Nippon Kayaku Co., Ltd.).

The thermoplastic polymer added to the resin composition for artificial marble as required is not particularly limited, but examples thereof include (meth) acrylic polymers such as polymethylmethacrylate, and (meth) acrylate-styrene. Copolymer, polystyrene, polyvinyl acetate, styrene-vinyl acetate copolymer, polyvinyl chloride, polybutadiene,
Conventionally known low-shrinkage polymers such as polyethylene, polycaprolactam and saturated polyester may be used alone or in combination. However, if a large amount of thermoplastic polymer for low shrinkage is blended, the viscosity during kneading will increase, making it difficult to obtain a casting compound with a high filler content, and in terms of product transparency and heat resistance. Sometimes you can only get inferior ones. Therefore, the thermoplastic polymer for low shrinkage may be used in a small amount as much as possible and is not particularly limited. However, the polymer B, a vinyl-based monomer having one polymerizable unsaturated group in one molecule and a polyfunctional monomer are used. It is preferably used within a range of 100% by weight or less based on the total amount of vinyl monomers.

Next, the polymer C having a carboxyl group according to the present invention will be described. As the compound (i) having two reactive groups, a functional group capable of reacting with a hydroxyl group and a carboxyl group, in one molecule, which is reacted with the polymer A having a hydroxyl group when the polymer C is synthesized, ,
Although not particularly limited, for example, oxalic acid, malonic acid,
Dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, phthalic acid, maleic acid, fumaric acid, itaconic acid, chloroacetic acid, bromoacetic acid And halogen-substituted carboxylic acid. in this way,
The two reactive groups having a functional group capable of reacting with a hydroxyl group and a carboxyl group, which the compound (i) has, may be two carboxyl groups, or a functional group other than a carboxyl group such as a halogen group and a carboxyl group. It may be a combination of groups. An acid anhydride may be used instead of the compound (i), or the compound (i) and an acid anhydride may be used in combination. The acid anhydride is not particularly limited, and examples thereof include succinic anhydride, glutaric anhydride, phthalic anhydride, maleic anhydride, and itaconic anhydride.

In the reaction of the polymer A having a hydroxyl group with the compound (i) and / or the acid anhydride, it is free to use a solvent or a conventionally known catalyst. Examples of this catalyst include inorganic acids such as sulfuric acid and hydrochloric acid, inorganic bases such as sodium hydroxide and potassium hydroxide when the functional group capable of reacting with the hydroxyl group contained in the compound (i) is a carboxyl group. Examples thereof include tertiary amine compounds such as triethylamine and pyridine, organic acid salts such as sodium acetate and potassium acetate, and in the case of a halogen group, tertiary amine compounds such as pyridine and triethylamine.

When the functional group capable of reacting with the hydroxyl group contained in the compound (i) is a carboxyl group (for example, when the compound (i) is a dibasic acid), the reaction temperature is not particularly limited, but 60 -100 degreeC is preferable. When the temperature is lower than 60 ° C, the reaction rate is slow and the final conversion rate is low.
Further, when the temperature exceeds 100 ° C., the reaction rate of the dibasic acid increases, but the amount of diester produced increases, which causes a problem that the molecular weight after the reaction increases.

Next, a polymer C having a carboxyl group according to the present invention and a compound (l) having two or more functional groups capable of reacting with a carboxyl group in one molecule are included as essential components. The resin composition to be used will be described. The polymer C having a carboxyl group may be used alone or in combination of two or more. The weight ratio of the polymer C and the compound (l) (polymer C / compound (l)) contained in this resin composition is not particularly limited, but is 99.99 / 0.01 to 40 /. It is preferably 60, and more preferably 99.9 / 0.1-60 / 40.

The compound (l) having two or more functional groups capable of reacting with a carboxyl group in one molecule is not particularly limited, but for example, a compound having two or more epoxy groups in one molecule, 1 Compound having two or more hydroxyl groups in molecule, compound having two or more amino groups in one molecule, compound having two or more mercapto groups in one molecule, two or more halogen groups in one molecule A compound having
A compound having two or more oxazoline groups in one molecule,
A compound having two or more aziridine groups in one molecule, 1
Examples thereof include compounds having two or more ester groups in a molecule, compounds having two or more carboxyl groups in a molecule, and the like.

The polymer C may be used as an essential component of the epoxy resin composition. The epoxy resin which is another essential component contained in such an epoxy resin composition is not particularly limited as long as it is a conventionally known epoxy resin, and for example, bisphenol A, bisphenol F, phenol novolac, cresol novolac, Examples include glycidyl ethers of phenols such as brominated bisphenol A; glycidyl ethers of alcohols such as butanol, butanediol, polyethylene glycol, polypropylene glycol; glycidyl esters of acids such as hexahydrophthalic acid and dimer acid. . These may be used alone or in combination of two or more.

Additives such as fillers, pigments and curing agents can be freely added to the epoxy resin composition as required. As the filler, aluminum hydroxide,
Magnesium hydroxide, calcium hydroxide, calcium carbonate, talc, clay, silica, kaolin, titanium oxide,
Quartz, quartz glass, alumina, zirconia, glass powder, glass fiber, marble, limestone, pyroxene, amphibole, sandstone, granite, natural crushed stone such as basalt, unsaturated polyester resin, thermosetting acrylic resin and melamine resin, etc. Examples include crushed synthetic resins. Examples of the curing agent include linear aliphatic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine; various polyamides having different amine values; mensendiamine, isophoronediamine, bis (4- Alicyclic amines such as aminocyclohexyl) methane; m-xylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone,
Aromatic amines such as m-phenylenediamine; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, dodecylsuccinic anhydride, pyropyrohydrate Acid anhydrides such as mellitic acid, methylcyclohexene tetracarboxylic anhydride, trimellitic anhydride, polyazelainic anhydride; phenolic hydroxyl group-containing compounds such as phenol novolac and cresol novolac; polymercaptans; 2,
4,6-tris (dimethylaminomethyl) phenol,
Anionic polymerization catalysts such as 2-ethyl-4-methylimidazole; Cationic polymerization catalysts such as BF ₃ monoethylamine complex; Dicyandiamide, amine adduct, hydrazide, amidoamine, blocked isocyanate, carbamate, ketimine, aromatic diazonium salt, etc. Examples of the latent curing agent include those listed above, and one or more of them can be used.

Next, the polyurethane of the present invention will be described. Used in synthesizing this polyurethane 1
The polyfunctional isocyanate compound (e) having two or more isocyanate groups in the molecule is as described above. The polyol component (j) containing the polymer A as an essential component is not particularly limited as long as it is a polyol other than the polymer A, but if necessary, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4 -Low molecular weight polyols such as butanediol, 1,3-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and sorbitol, and partial esterified products of low molecular weight polyols such as sorbitan fatty acid ester, polyethylene glycol, polypropylene glycol Polyether glycols such as polypropylene glycol-polyethylene glycol block copolymers, low molecular weight polyols described above and phthalic acid, phthalic anhydride, terephthalic acid, maleic acid, maleic anhydride Polyester polyol synthesized from polyfunctional carboxylic acid such as acid, fumaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, polycarbonate polyol, butadiene and diene polyol consisting of butadiene / acrylonitrile copolymer main chain, polyolefin polyol 1 selected from polymer polyols such as acrylics, acrylic polyols and polymer polyols
One kind or a combination of two or more kinds of polyols can be used.

In this synthesis, the total amount of the polyol component (j) and the polyfunctional isocyanate compound (e) may be reacted in one step, or the polyol component (j) may be reacted in the first step. ) And a polyfunctional isocyanate compound (e) are reacted with each other to synthesize a polymer (oligomer) having at least two isocyanate groups at terminals, and then the polymer (oligomer) is added in the next step. May be used in combination with another polymer having one hydroxyl group (oligomer) to synthesize polyurethane. However, in the case of the two-step reaction, it may be necessary to remove the isocyanate compound remaining after the reaction on the way out of the system.

When synthesizing the polyurethane of the present invention,
The ratio of the amounts of the polymer A and the polyfunctional isocyanate compound (e) used is not particularly limited. For example, in the case of the above two-step reaction, the molar ratio of the isocyanate group in the compound (e) to the hydroxyl group in the polymer A (NCO /
OH) is not a problem as long as it is higher than 1, but in order to prevent the increase in molecular weight at this stage and synthesize polyurethane having a clear block structure, 1.2 to 2.0 is preferable, and 1.5 to 2.0 is more preferable. Further, the molar ratio of the isocyanate group in the polyfunctional isocyanate compound (e) and the hydroxyl group in the polymer A in the case of the one-step reaction (NCO
/ OH) is preferably 0.5 to 1.5,
It is more preferably 0.8 to 1.2.

When synthesizing the polyurethane of the present invention,
In order to accelerate the urethanization reaction, it is free to use known catalysts such as organotin compounds and tertiary amines, or use various solvents. Next, the polyester of the present invention will be described. The polyol component (j) containing the polymer A as an essential component, which is used when synthesizing this polyester, is the same as that described for the polyurethane. Further, the compound (g) having two or more carboxyl groups in one molecule is also the same as described above.

In this synthesis, it is free to use a known catalyst such as an inorganic acid such as sulfuric acid or any of various solvents to accelerate the esterification reaction. When the polyurethane or polyester of the present invention is used as a molding material, the molding material may include glass fibers such as those contained in conventional molding materials as other components, if necessary.
Fillers such as pulp, mold release agents, pigments such as calcium carbonate and titanium oxide, ultraviolet absorbers, antioxidants and the like may be contained. As a molding method, any conventionally known molding method may be used. Regarding the shape of the molded product, it can be molded into various shapes such as a film shape and a sheet shape.

Next, a block polymer containing the polymer A as an essential component according to the present invention will be described. The method for obtaining this block polymer is not particularly limited, but examples thereof include the following four methods. Two or more kinds of polyols are used as the polyol component (l) containing the polymer A as an essential component obtained by the production method of the present invention, and a compound having two or more functional groups capable of reacting with the hydroxyl group in one molecule. How to react with.

The polymer A obtained by the production method of the present invention is reacted with a polymer having only one hydroxyl group in one molecule and a compound having two or more functional groups capable of reacting with the hydroxyl group in one molecule. How to make. A method of reacting the polymer A obtained by the production method of the present invention with a polymer having one or two or more functional groups capable of reacting with a hydroxyl group in one molecule.

A method of ring-opening polymerizing one or more cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran using the polymer A obtained by the production method of the present invention as an initiator. In the above method, and, as the functional group capable of reacting with a hydroxyl group, is not particularly limited, for example,
Isocyanate group, carboxyl group, triazine ring, methylolated triazine ring, acid anhydride, azlactone ring,
Examples thereof include silanol groups, carbonate groups, epoxy groups, acid halide groups and the like.

The method of the reaction in the above and the above methods is not particularly limited, but for example, any of the one-step reaction method and the multi-step reaction method described in the above description of polyurethane and polyester may be used. be able to. The use of the block polymer of the present invention is not particularly limited, but examples thereof include surfactants, compatibilizers, toner resins, hot melt adhesives, thermoplastic elastomers, thermosetting elastomers, resin modifiers, and adhesives. Agents, dispersants, heat resistant transparent resins, impact resistant transparent resins, artificial leather, synthetic leather, cement water reducing agents, urethane foams and the like.

The structure of the block polymer of the present invention is not particularly limited, but is naturally determined according to each application. For example, in the case of using a surfactant as an example, it is desirable that two or more kinds of segments constituting the block polymer are composed of a hydrophilic segment and a hydrophobic segment. For example, in the case of using an elastomer, two or more kinds of segments constituting the block polymer have glass transition temperatures of 10 or less.
It is desirable that they differ by not less than ° C.

[0092]

In the production method of the present invention, other than the vinyl-based monomer (a), the alcohols (b) in which the polyfunctional alcohol is essential, and the initiator system (c) in which hydrogen peroxide is essential in the reactor. By substantially not containing the component (1), it is possible to introduce hydroxyl groups at both ends of the polymer and at least two hydroxyl groups at at least one end. That is, since hydrogen peroxide used as an essential component of the initiator system (c) has extremely high polarity, it is not compatible with many vinyl monomers and OH radicals generated by decomposition of hydrogen peroxide. Cannot initiate polymerization effectively.
However, the use of a polyfunctional alcohol facilitates compatibilization and enables reliable introduction of hydroxyl groups.

Further, since the OH radicals generated by the decomposition of hydrogen peroxide are extremely unstable, side reactions such as hydrogen abstraction reaction (chain transfer reaction) and oxidation reaction easily occur, and a hydroxyl group is attached to the end of the polymer. Although it is difficult to surely introduce the hydroxyl group, coexistence of the polyfunctional alcohol improves the selectivity of the reaction, and the hydroxyl group can be reliably introduced.

Further, since the polyfunctional alcohol has a high boiling point, there is no particular restriction on the reaction temperature, which is very advantageous for carrying out the polymerization reaction. The polymer A obtained by the production method of the present invention has transparency, weather resistance, water resistance and hydrolysis resistance by arbitrarily selecting the type of the vinyl-based monomer (b) constituting the main chain. It has chemical resistance,
Characteristic that various resins such as polyester resin, polyurethane resin, polycarbonate resin and the like derived from the composition containing the polymer A, various block polymers, and the like are very stretchable (having good bending workability) and strong. Since it exerts the effect of paint, elastic wall material, coating waterproof material, adhesive, floor material, tackifier, adhesive, binder (magnetic recording medium, ink binder, casting binder,
Baking brick binder, graft material, microcapsule, glass fiber sizing, etc.), sealing material,
Urethane foam (hard, semi-hard, soft), urethane R
IM, UV / EB curable resin, high solid paint, thermosetting elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coating agent,
Resin for artificial marble, impact resistance additive for artificial marble, resin for ink, film (laminate adhesive, protective film, etc.), resin for laminated glass, reactive diluent, various molding materials, elastic fiber, artificial leather, synthetic It is very useful as a raw material for leather and the like, and as various resin additives and raw materials thereof.

The polymer A is prepared by reacting the hydroxyl groups at both ends with an appropriate method to obtain another functional group (for example, a polymerizable unsaturated group such as vinyl group, formyl group, amino group,
Carboxyl group, ethynyl group, epoxy group, silanol group, alkoxysilyl group, hydrosilyl group, mercapto group, oxazoline group, maleimide group, azlactone group,
Lactone group, bromine, chlorine, etc.) at both ends, and
At least two other functional groups at least at one end
It is possible to easily convert it into a polymer having a single component.
These polymers are also very useful. For example, a polymer having a carboxyl group at both ends and at least two carboxyl groups at at least one end (polymer C) is very effective as an impact resistance imparting agent for epoxy adhesives. Further, the polymer A becomes a raw material for a surfactant, a urethane foam, a cement water reducing agent, etc. by adding a plurality of ethylene oxide or propylene oxide to the terminal hydroxyl group.

A composition essentially containing the polymer A and the polyfunctional isocyanate compound (e), and the polymer A
When the composition containing the aminoplast resin (f) and the aminoplast resin (f) is used as a coating material, it is not only flexible and tough, but also has excellent weather resistance, water resistance, hydrolysis resistance, chemical resistance and hardness. An excellent coating film can be obtained.

When a composition essentially containing the polymer A and the polyfunctional isocyanate compound (e) is used as a sealing material, it is very flexible and tough, and has weather resistance, water resistance,
A sealing material having excellent chemical resistance can be obtained.
When a composition essentially containing the polymer A and the polyfunctional isocyanate compound (e) is used for urethane foam applications and thermosetting polyurethane elastomer applications, the urethane foam has excellent flexibility, weather resistance, water resistance and chemical resistance. And an elastomer can be obtained.

A polymerizable group obtained by reacting the polymer A with a compound (h) having two kinds of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group, in one molecule. When a composition containing, as an essential component, a vinyl-based monomer having at least one polymerizable unsaturated group in one molecule in addition to the polymer B having a saturated group is used for the gel coat resin composition application, the gel coat layer The reaction shrinkage during molding is small, the viscosity of the gel coat resin composition during work is low, the workability of gel coat is good, and the hardness is high, and a tough gel coat layer having good weather resistance is obtained.

Polyurethane obtained by reacting the polymer A with the polyfunctional isocyanate compound (e), and
When a polyester obtained by reacting the polymer A with a compound (g) having two or more carboxyl groups in one molecule is used as an essential component of a molding material, processability, hydrolysis resistance, and weather resistance are obtained. It is possible to obtain a molding material having excellent properties, chemical resistance and low temperature characteristics.

[0100]

EXAMPLES Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. Moreover, in the following Examples and Comparative Examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively. -Example 1-A flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, and a reflux condenser was charged with 100 parts of butyl acrylate, 4 parts of ethylene glycol, and 3.6 parts of 60% hydrogen peroxide solution, After replacing the nitrogen in the flask, the mixture was heated to 140 ° C. while gently blowing nitrogen gas, and kept at the same temperature for 10 minutes.
The stirring was continued for a minute to complete the polymerization. When the polymerization rate was calculated from the residual rate of butyl acrylate by a gas chromatogram, it was 92%.

Then, the polymer was extracted and separated from the reaction mixture containing the polymer using a toluene / water-based extraction solvent to obtain a toluene solution containing the polymer. Toluene was distilled off, and the residue was dried at 45 ° C. under reduced pressure to obtain a purified polymer [1]. The number average molecular weight (Mn) of the purified polymer [1] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and was 15,000. The average number of terminal hydroxyl groups (Fn (OH)) of the polymer [1] is JIS-K-1.
Based on the OH value determined according to 557 and the value of the number average molecular weight measured above, the result was 3.3 (mol / polymer 1 mol).

Example 2-Vinyl type monomer (a), polyalcohol essential alcohols (b) and hydrogen peroxide essential initiator system (c) in Example 1, The polymerization reaction was performed in the same manner as in Example 1 except that the ratios were set as shown in Table 1 below. Then, in the same manner as in Example 1, a purified polymer [2] was obtained.

The number average molecular weight of the polymer [2] after purification (M
n) is measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and the average number of terminal hydroxyl groups (Fn (OH)) is measured according to JIS-K-155.
It was calculated based on the OH value determined according to 7 and the value of the number average molecular weight measured above. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1.

Example 3-67 parts of ethylene glycol was charged into a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, and the inside of the flask was replaced with nitrogen. Then, while gently blowing nitrogen gas, The temperature is raised to 140 ° C. After the temperature in the reaction vessel became stable, a mixed solution of 60 parts of butyl acrylate and 40 parts of methyl methacrylate dissolved with 1.7 parts of dodecylbenzenesulfonic acid, 3.2 parts of 60% hydrogen peroxide solution and ethylene. After the mixture with 33 parts of glycol was added dropwise over 1 hour, stirring was continued at 140 ° C. for 10 minutes to complete the polymerization. Then, a purified polymer [3] was obtained by the same purification method as in Example 1.

The number average molecular weight of the polymer [3] after purification (M
n) is measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and the average number of terminal hydroxyl groups (Fn (OH)) is measured according to JIS-K-155.
It was calculated based on the OH value determined according to 7 and the value of the number average molecular weight measured above. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1.

Example 4-A polymerization reaction was carried out in the same manner as in Example 3 except that the kinds of vinyl monomers and alcohols were changed as shown in Table 1 below. Then, a purified polymer [4] was obtained by the same purification method as in Example 1. The number average molecular weight (Mn) of the purified polymer [4] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and the average number of terminal hydroxyl groups (Fn (O
H)) was calculated based on the OH value determined according to JIS-K-1557 and the value of the number average molecular weight measured above.
The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1.

-Examples 5 to 7-Sumitomo / Sulzer SMX type element (manufactured by Sulzer) and a reaction tube equipped with an outer jacket (internal diameter 4
2.7 mm, length 450 mm, number of elements 12, SU
In a tubular reactor in which 5 S316 products (substantial internal volume 190 ml) were connected, the vinyl-based monomer (a), the alcohols (b) containing the polyfunctional alcohol as an essential component and the peroxide were added at the ratios shown in Table 2 below. 32 ml of a mixture of an initiator system (c) which essentially requires hydrogen oxide using a plunger pump
It is continuously supplied at a flow rate of / min, and a heating medium is flown in the jacket so that the internal temperature is stable at the polymerization temperature shown in Table 2 below.
Continuous polymerization was performed. The average residence time was 30 minutes. Then, purification was carried out by the same purification method as in Example 1 to obtain polymers [5] to [7].

The number average molecular weight (Mn) of the purified polymers [5] to [7] was measured by gel permeation chromatography (GP).
The average number of terminal hydroxyl groups (Fn (OH)) is measured according to JIS-
It was calculated based on the OH value determined according to K-1557 and the value of the number average molecular weight measured above. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1.

Example 8-Vinyl type monomer (a), alcohols (b) requiring polyfunctional alcohol and initiator system (c) requiring hydrogen peroxide in Example 5, The ratio and the polymerization temperature are as shown in Table 3 below, and 30% of the vinyl-based monomer (a) and the initiator system (c) containing hydrogen peroxide as an essential component was added immediately before the third reaction tube. A polymer [8] was obtained in the same manner as in Example 5, except that the flow rate was 6.4 ml / min by the plunger pump.

The number average molecular weight of the polymer [8] after purification (M
n) is measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and the average number of terminal hydroxyl groups (Fn (OH)) is measured according to JIS-K-155.
It was calculated based on the OH value determined according to 7 and the value of the number average molecular weight measured above. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1.

-Examples 9 and 10-A twin-screw extruder equipped with an external jacket (inner diameter 1 inch, L / D = 48, barrel number 8, screw SACM645, shaft SNC
M439, other SACM645), a vinyl-based monomer (a) in the ratios shown in Table 3 below, alcohols (b) requiring a polyfunctional alcohol, and an initiator system (requiring hydrogen peroxide) ( The mixture of c) was continuously supplied using a plunger pump at a flow rate of 20 ml / min, and the screw shape and rotation speed were determined so that the average residence time in a steady state was about 30 minutes. A heating medium was flowed in the jacket so that the internal temperature was stabilized at the polymerization temperature shown in Table 3 below, and continuous polymerization was carried out.

Polymer after purification

The number average molecular weight (Mn) of [9] and [10] was measured by gel permeation chromatography (GP
The average number of terminal hydroxyl groups (Fn (OH)) is measured according to JIS-
It was calculated based on the OH value determined according to K-1557 and the value of the number average molecular weight measured above. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1.

Example 11-Vinyl type monomer (a), polyalcohol essential alcohols (b) and hydrogen peroxide essential initiator system (c) in Example 9, The ratio and the polymerization temperature are as shown in Table 4 below, and 50% of the vinyl-based monomer (a) and the initiator system (c), which essentially requires hydrogen peroxide, was fed from the raw material supply port at the center of the extruder. Other than continuously supplying 6.6 ml / min by a plunger pump,
A polymer [11] was obtained in the same manner as in Example 9.

The number average molecular weight (Mn) of the purified polymer [11] was measured by the standard polystyrene conversion method using gel permeation chromatography (GPC), and the average number of terminal hydroxyl groups (Fn (OH)) was JIS-K-1
It was calculated based on the OH value determined according to 557 and the value of the number average molecular weight measured above. The results are shown in Example 1.
The polymerization rates obtained in the same manner as above are shown in Table 6 below.

-Examples 12 to 14-KRC kneader with an outer jacket equipped with a raw material supply port and a product extraction port (inner diameter 2 inches, L / D = 13.2, effective internal volume 1.2 L, Kurimoto Tekko Co., Ltd.) (Manufactured), vinyl-based monomers (a) in the ratios shown in Tables 4 and 5 below, alcohols (b) that require polyfunctional alcohols, and initiator systems (c) that require hydrogen peroxide. Was continuously supplied at a flow rate of 20 ml / min using a plunger pump, the paddle rotation speed was 20 rpm, the average residence time in the steady state was 30 minutes, and the internal temperature was as shown in Tables 4 and 5 below. A heating medium was flowed in the jacket so that the polymerization temperature became stable at the polymerization temperature shown in, and continuous polymerization was carried out.

The number average molecular weight (Mn) of the purified polymers [12] to [14] was measured by gel permeation chromatography (G).
The average number of terminal hydroxyl groups (Fn (OH)) is measured according to JIS according to JIS.
It was calculated based on the OH value determined according to -K-1557 and the value of the number average molecular weight measured above. The results
The polymerization rates obtained in the same manner as in Example 1 are shown in Table 6 below.

Comparative Example 1 Comparative Example 1 was repeated except that 3.5 parts of azobisisobutyronitrile (AIBN) was used in place of the hydrogen peroxide solution as the initiator. A polymer [1] for use was obtained. The number average molecular weight and the average number of terminal hydroxyl groups (Fn (OH)) of the obtained comparative polymer [1] were determined in the same manner as in Example 1. The number average molecular weight was 18,000.
And the average number of terminal hydroxyl groups (Fn (OH)) was 0.1. The results are shown in Table 8 below together with the polymerization rate obtained in the same manner as in Example 1.

-Comparative Example 2-In Example 3, the types of the vinyl-based monomer (a), the alcohols (b) containing a polyfunctional alcohol as an essential component, and the initiator system (c) containing a hydrogen peroxide as an essential component. , Table 7 below
And (a), (b),
A comparative polymer [2] was obtained in the same manner as in Example 3 except that 50 parts of toluene was used as a component (solvent) other than (c).

The number average molecular weight and the average number of terminal hydroxyl groups (Fn (OH)) of the obtained comparative polymer [2] were determined in Example 1.
The number average molecular weight was 2200, and the average number of terminal hydroxyl groups (Fn (OH)) was 0.5. The results are shown in Table 8 below together with the polymerization rate obtained in the same manner as in Example 1. -Comparative Example 3- In Example 5, the types and ratios of the vinyl-based monomer (a), the alcohols (b) requiring the polyfunctional alcohol and the initiator system (c) requiring the hydrogen peroxide were determined as follows. Table 7 below
And (a), (b),
A comparative polymer [3] was obtained in the same manner as in Example 5 except that the mixture of 100 parts of (c) and 100 parts of toluene was continuously fed to the reactor.

The number average molecular weight and the average number of terminal hydroxyl groups (Fn (OH)) of the obtained comparative polymer [3] are shown in Example 1.
The number average molecular weight was 4,800 and the average number of terminal hydroxyl groups (Fn (OH)) was 0.6. The results are shown in Table 8 below together with the polymerization rate obtained in the same manner as in Example 1. —Example 15— 100 parts of the polymer [1] obtained in Example 1 and 2.4 parts of hexamethylene diisocyanate (NCO / OH = 1.
05 (molar ratio)), 200 parts of methyl isobutyl ketone and 0.1 part of dibutyltin dilaurate were charged, well stirred, and then coated on a Teflon plate so that the film thickness was 500 μ or less, and reacted at 80 ° C. for 5 hours. Then, toluene was cast to obtain a crosslinked polyurethane [15].

Gel fraction of the polyurethane [15] (TH
The weight fraction of the insolubles in F) was measured and found to be 91%. It was found that hydroxyl groups were certainly attached to the ends of the polymer. Example 16 In Example 15, instead of 100 parts of the polymer [1], 65 parts of the polymer [1] and 35 parts of the polymer [2] obtained in Example 2 were used, and the amount of hexamethylene diisocyanate was 2 parts. The same operation as in Example 15 was carried out except that the amount was changed to 1 part to obtain a crosslinked polyurethane [16].

The gel fraction (TH
The weight fraction of the insoluble matter (F) was measured and found to be 92%. It was found that a hydroxyl group was certainly attached to the end of the polymer. -Example 17-In Example 15, 50 parts of polymers [1] and 50 parts of polymers [2] obtained in Example 2 were used instead of 100 parts of polymers [1], and the amount of hexamethylene diisocyanate was set to 1. The same operation as in Example 15 was carried out except that the content was changed to 0.9 part to obtain a crosslinked polyurethane [17].

Gel fraction of the polyurethane [17] (TH
The weight fraction of the insolubles in F) was measured and found to be 91%. It was found that hydroxyl groups were certainly attached to the ends of the polymer. Example 18 In Example 15, 70 parts of polymer [1] and 0.51 part of 1,4-butanediol were used instead of 100 parts of polymer [1], and the amount of hexamethylene diisocyanate was 2.7 parts. The same operation as in Example 15 was carried out except that the above was carried out to obtain a crosslinked polyurethane [18].

Gel fraction of the polyurethane [18] (TH
The weight fraction of the insoluble matter (F) was measured and found to be 98%. It was found that a hydroxyl group was surely attached to the end of the polymer. -Example 19- Methyl ethyl ketone 100 was put into a flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, a dropping funnel and a reflux condenser.
And 2.0 parts of hexamethylene diisocyanate were charged and heated to a temperature at which reflux was applied (about 80 ° C.), and then 60 parts of Byron GK130 (polyester diol, manufactured by Toyobo Co., Ltd., Mn = 6000) and dibutyl were added. 0.1 parts of tin dilaurate to 200 parts of methyl ethyl ketone
What was melt | dissolved in 1 part was dripped over 1 hour, and also the reaction was completed by continuing stirring at the same temperature for 3 hours, and the methyl ethyl ketone solution of the polyester which has an isocyanate group at both ends was obtained.

Then, the polymer [2] obtained in Example 2 was obtained.
A solution prepared by dissolving 145 parts and 0.1 part of dibutyltin dilaurate in 100 parts of methyl ethyl ketone was added dropwise to this flask over 1 hour, and then the same operation as in Example 15 was performed to cast methyl ethyl ketone at the same temperature for 3 hours. Thus, a crosslinked polyurethane [19] was obtained.

Example 20 A flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, a dropping funnel and a reflux condenser was charged with 100 parts of toluene and 3.5 parts of hexamethylene diisocyanate and heated to 80 ° C. , The polymer obtained in Example 2 [2]
A solution prepared by dissolving 254 parts and 0.1 part of dibutyltin dilaurate in 100 parts of toluene was added dropwise over 1 hour, and stirring was continued at the same temperature for 3 hours to complete the reaction,
A toluene solution of a polymer having at least two isocyanate groups at the ends was obtained.

Next, the polymer [1] obtained in Example 1 was obtained.
A solution prepared by dissolving 145 parts and 0.1 part of dibutyltin dilaurate in 100 parts of toluene was added dropwise to this flask over 1 hour, the same operation as in Example 15 was performed, and toluene was cast at the same temperature for 3 hours. A crosslinked polyurethane [20] was obtained. -Example 21- 100 parts of polymers [1] and phthalic anhydride 2.1 in the flask provided with the stirrer, the thermometer, the azeotropic dehydration tube, and the reflux condenser.
Parts and 5 parts of xylene were charged, and the mixture was thoroughly stirred, and first dehydrated from the azeotropic dehydration tube at 100 ° C. for 2 hours, then 1
The same operation as in Example 15 was performed at 60 ° C. for 2 hours, and finally the reaction was performed at 220 ° C. for 1 hour.
A crosslinked product of 1] was obtained.

Example 22 In Example 21, instead of 100 parts of the polymer [1], 65 parts of the polymer [1] and 35 parts of the polymer [2] obtained in Example 2 were used. Amount 1.8
The same operation as in Example 21 was carried out except for using parts to obtain a crosslinked polyester [22].

Example 23 In place of 100 parts of the polymer [1] in Example 21, 50 parts of the polymer [1] and 50 parts of the polymer [2] obtained in Example 2 were used. Amount 1.7
The same operation as in Example 21 was carried out except that a part was added to obtain a crosslinked polyester [23].

Example 24 In Example 21, 65 parts of polymer [1] and 1.6 parts of 1,4-butanediol were used in place of 100 parts of polymer [1], and the amount of phthalic anhydride was adjusted to 4 parts. The same operation as in Example 21 was carried out except that the content was adjusted to 0.0 part to obtain a crosslinked product of polyester [24].

Example 25 Resin for acrylic primer (composition (wt%): ethyl acrylate / styrene / butyl acrylate / methacrylic acid / 2-hydroxyethyl acrylate / methyl methacrylate = 35/35/12/8 / 6/3, number average molecular weight 15
000, hydroxyl value 36, acid value 50) 100 parts alkylmer aminoformaldehyde resin Cymel 325 (manufactured by Mitsui Cyanamide Co., Ltd.) 30 parts, para-toluene sulfonic acid 0.25 part curing accelerator, rust preventive pigment As zinc chromate, 30 parts of cyclohexanone as solvent, and 50 parts of acid value titanium were well mixed with stirring, and chromated in advance to 0.5 mm
It was applied to a thick galvanized steel sheet with a bar coater so that the dry film thickness was 5 μm, and baked at 220 ° C. for 1 minute.

After cooling, 100 parts of the polymer [12] obtained in Example 12, 30 parts of Cymel 325 (manufactured by Mitsui Cyanamide Co., Ltd.) as an alkyl etherified aminoformaldehyde resin, and a curing accelerator were coated on the primer coating film. As a dry film, 0.25 parts of paratoluenesulfonic acid, 125 parts of titanium oxide, 0.5 parts of a leveling agent MK Conk (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.), and 400 parts of cyclohexanone were well stirred and mixed with a paint shaker. Apply with a bar coater to a thickness of 25μ,
After setting at 0 ° C for 10 minutes, it was baked at 235 ° C for 60 seconds to prepare a coated steel sheet. Then, the coin scratch resistance of this coating film was evaluated as follows.

Further, without using the acrylic primer resin, the polymer obtained in Example 12 was directly applied to a zinc-plated steel sheet having a thickness of 0.5 mm which had been previously chromated.
2] 100 parts, Cymel 325 (manufactured by Mitsui Cyanamid Co., Ltd.) as an alkyl etherified aminoformaldehyde resin, 0.25 part of paratoluenesulfonic acid as a curing accelerator, 125 parts of titanium oxide, a leveling agent MK Conc (Kyoeisha Yushi Yushi 0.5 parts by Chemical Industry Co., Ltd.,
A mixture of 400 parts of cyclohexanone, which was well stirred and mixed with a paint shaker, was applied with a bar coater so that the dry film thickness was 25 μm, set at 70 ° C. for 10 minutes, and then baked at 235 ° C. for 60 seconds to prepare a coated steel sheet. . And the following (1)-(6) was evaluated about this coating film. (1) Coin Scratch Property The state of the coated film after visually strongly scratching the coated steel plate coating with a 10-yen coin was visually determined.

∘: The primer does not peel off from the base material (steel plate), the interlayer adhesion between the primer and the topcoat is good, and only the topcoat undergoes cohesive failure. ◯: The primer is slightly peeled from the substrate, but the interlayer adhesion between the primer and the top coat is good. Δ: The primer does not peel from the substrate, but the interlayer adhesion between the primer and the topcoat is poor and the topcoat easily peels off.

X: The top coat is peeled off from the substrate together with the primer. Inadequate adhesion of primer to substrate. XX ... The top coat with the primer peels off significantly from the substrate. (2) Workability (T vent) The coated steel sheet was bent from 180 degrees 4T to 0T sequentially, and cracks generated in the bent portion were observed and judged with a magnifier of 15 times.
For example, if a crack occurs when three copper plates with the same plate thickness are sandwiched between the bent parts and bent, the workability is T-vent 3T.
Therefore, the smaller T-vent number indicates the better workability. (3) Adhesiveness A cross-cut first-eye peeling test was performed according to JIS D-0202. (4) Boiling water resistance test The coated steel sheet was immersed in ion-exchanged water, boiled for 8 hours, then taken out, and the coating film was observed and judged.

B: No blister, adhesion 100 /
100 △ ・ ・ ・ Blisters occurred × ・ ・ ・ Blisters occurred remarkably. (5) Touch resistance The coated steel sheet was cross-cut with a cutter knife to JIS.
According to K-5400, a salt spray test was performed for 500 hours, and then the cross-cut portion was peeled off with cellophane tape, and the peeling width was evaluated. (6) Pencil hardness It was performed according to JIS-K-5400 using a Mitsubishi Uni-Pencil.

The test results are summarized in Table 9 below. The top coat using the telechelic polymer of the present invention has excellent adhesion to a primer, is not easily scratched, is flexible and has excellent processability, and is also excellent in boiling water resistance and touch resistance. I understood it. -Comparative Examples 4 and 5-Example 2 except that the polymer [12] used in the coating material for the top coat in Example 25 was as shown in Table 9 below.
The same operation as 5 was repeated to prepare a coated steel sheet for comparison. The test results of the coating film are summarized in Table 9 below.

Example 26-To 100 parts of the polymer [8] obtained in Example 8 was added trimethylolpropane with 3 equivalents of tolylene diisocyanate (Coronate L (manufactured by Nippon Polyurethane Co.), 5 parts of Coronate L) was mixed and diluted with ethyl acetate to a 20% solution to obtain an adhesive solution. A 12 μm thick polyerylene terephthalate film (hereinafter abbreviated as PET) as an adherend and a 50 μm thick unstretched polypropylene film subjected to corona discharge treatment (hereinafter CP
For the purpose of laminating them, the above adhesive solution is applied to both of them by a dry laminator so that the solid content is 3.0 g / m ² , the solvent is volatilized, and then they are laminated. . At that time, the wetting property of the adhesive solution was examined. The resulting laminated film is 15 mm wide
Cut into test pieces of 300m with a tensile tester
A T-type peel test was performed at m / min to measure the initial adhesive force.
Moreover, after laminating, a test piece was prepared from a laminate film obtained by curing at 50 ° C. for 3 days, and the normal state adhesive strength, hot water resistance, chemical resistance and flexibility were evaluated by the following methods. The results are shown in Table 10 below. (1) Normal-state adhesive force A T-type peel tester similar to the initial adhesive force was used. (2) Hot Water Resistance and Chemical Resistance Test In the hot water resistance test, the test piece was put together with water in a 50 cc autoclave, treated at 120 ° C. for 5 hours, and then subjected to a T-type peel test to examine the peel state and strength. For the chemical resistance test, a T-type peel test was conducted on a test piece immersed in a 4% acetic acid aqueous solution at 25 ° C. for 4 hours. (3) Flexibility Flexibility was judged by the state of peeling in each peeling test. The meanings of the marks in the table are as follows.

◯: The peel strength is large and peeling occurs, and thus the uniform strength is exhibited. Δ: Partially strong, but easily peeled off. X: Peeling strength is small and easily peeled off. (4) Wetting characteristics (observation results) ◯: Uniform application is possible Δ: Partially repellent ×: Repellent The adhesive composition using the telechelic polymer of the present invention is initially used when used as an adhesive for lamination. In addition to having a strong adhesive strength in the normal state, it was also excellent in hot water resistance, chemical resistance and flexibility.

-Comparative Examples 6 and 7-A test piece of a comparative laminated film was prepared by repeating the same operation as in Example 26 except that the polymer shown in Table 10 below was used instead of the polymer [8]. Obtained. Table 10 below shows the evaluation results of the normal-state adhesive strength, hot water resistance, chemical resistance, and flexibility of the test pieces.

-Example 27- To 35 parts of the polymer [7] obtained in Example 7, 35 parts of ethyl acetate, 30 parts of toluene, and Coronate L (isocyanate compound manufactured by Nippon Polyurethane Co., Ltd.) were added and stirred well. A 25 μm-thick PET film was applied so that the thickness after drying was 25 μm, and heat-dried at 100 ° C. for 3 minutes to obtain a pressure-sensitive adhesive sheet.

With respect to this pressure-sensitive adhesive sheet, the adhesive strength at 23 ° C. and 5 ° C., the initial tack and the adhesive holding power were measured by the following methods, and the results shown in Table 11 below were obtained. Adhesive strength : Test pressure-sensitive adhesive sheet (25 ° C) in an atmosphere having a temperature of 23 ° C and a humidity of 65% and in an atmosphere having a temperature of 5 ° C.
mm width) is laminated on a polyethylene plate by reciprocating a 2 kg rubber roller once. After 25 minutes, the resistance value when peeled off at a speed of 300 mm / min in the 180 degree direction was measured.

Initial tack : temperature of 23 ° C. and humidity of 65%
Resistance when the test pressure-sensitive adhesive sheet was attached to a probe tack tester (manufactured by Nichiban Co., Ltd.) in an atmosphere of 5 ° C. and at a temperature of 5 ° C. and peeled off at a contact time of 1 second at a speed of 1 cm / second. The value was measured. Adhesive holding power : A test pressure-sensitive adhesive sheet is attached to a stainless steel plate (SUS304) in an area of 25 mm x 25 mm, and 20
After a lapse of minutes, a load of 1 kg was applied at 80 ° C., and the time until falling was measured.

The pressure-sensitive adhesive composition using the telechelic polymer of the present invention has an adhesive force at room temperature, probe tack,
Not only excellent holding power, but also adhesive strength especially at low temperature,
It was also excellent in probe tack. -Comparative Example 8-In Example 27, instead of the polymer [7], the following Table 1 was used.
The same operation as in Example 27 was repeated except that the polymer shown in 1 was used to obtain a pressure-sensitive adhesive sheet for comparison.

With respect to this pressure-sensitive adhesive sheet for comparison, the adhesive strength at 23 ° C. and 5 ° C., the initial tack and the adhesive holding power were measured by the following methods, and the results shown in Table 11 below were obtained. -Example 28-The polymer obtained in Example 9

[9] 100 parts of calcium carbonate 100 parts, titanium dioxide 15 parts, calcium oxide 20 parts, Disparlon 3600N (manufactured by Kusumoto Kasei Co., Ltd.)
2 parts, 0.5 part of dibutyltin dilaurate and 0.2 part of carbon black were well stirred with a kneader, and then 10.2 parts of hexamethylene diisocyanate was added.
An elastic sealant was obtained by thoroughly stirring with a kneader at 0 ° C. for 3 hours. The elastic sealant is JIS-A-
When the characteristic evaluation by 5757 and the weather resistance test shown below were performed, the results shown in Table 12 below were obtained. (1) Weather resistance test In a sunshine weather meter, a test piece (dumbbell) prepared in advance was allowed to stand still under the conditions of an atmospheric temperature of 63 ° C., UV irradiation, 1 cycle for 2 hours, and 18 minutes for rain for 1 cycle. After a lapse of time, the test piece (dumbbell) was taken out and its elongation storage rate (%) was measured.
The elongation retention was determined by the ratio of the maximum elongation before and after the weather resistance test. The results are shown in Table 12 below.

The elastic sealant composition using the telechelic polymer according to the present invention was excellent not only in elongation under normal conditions but also in weather resistance. -Comparative Examples 9 to 11-Polymer in Example 28

Table 1 below instead of [9]
The same operation as in Example 28 was repeated except that the polymer shown in 2 was used to obtain an elastic sealant for comparison. When the characteristics of the elastic sealant for comparison were evaluated according to JIS-A-5757, the results shown in Table 12 below were obtained.

Example 29 A mixture of 700 parts of the polymer [1] obtained in Example 1 and 6.1 parts of trimethylolpropane was dried by heating at 70 ° C. for 2 hours under a reduced pressure of 2 Torr. . Isolate to the dried and degassed polyol mixture.
143-L (Upjohn Polymer Chem
icals) 365 parts (isocyanate 2.56 meq / g) were added. This temperature was kept at 70 ° C. for 70 minutes to complete the reaction. This product is 2.2 meq / g
Isocyanate content and 20000 cp at 25 ° C
It was an almost colorless liquid with a viscosity of s. After storing the sample at 80 ° C for 2 weeks, the product was
The viscosity increased to 000 cps. Product 8 heated to 35 ° C
0 g of 100% of a 2% aqueous solution of Pluronic L-62, a nonionic surfactant manufactured by Wyandotte
By vigorously stirring with l, a flexible and supple flexible urethane foam was obtained. The physical properties are shown in Table 13 below.

Comparative Examples 12 to 14 In Example 29, the same operation as in Example 29 was repeated except that the type and amount of the polymer shown in Table 13 below was used instead of 700 parts of the polymer [1]. A soft urethane foam for comparison was obtained. The physical properties are shown in Table 13 below. -Example 30- (Synthesis of polymer B having a polymerizable unsaturated group) 100 parts of the polymer [13] obtained in Example 13 and maleic anhydride were placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. 4.
Charge 4 parts, dibutyltin oxide 0.1 part, hydroquinone 0.1 part and toluene 200 parts at 100 ° C.
After stirring for 5 hours to carry out the reaction, toluene was removed by an evaporator and a vacuum dryer to obtain a polymer [30].

Example 31- (Synthesis of Polymer B Having Polymerizable Unsaturated Group) 100 parts of the polymer [4] obtained in Example 4 was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. 2-Isocyanatoethyl methacrylate 12.9 parts, dibutyltin dilaurate 0.1 part, hydroquinone 0.1 part and toluene 20
0 part was charged, the mixture was stirred at 80 ° C. for 5 hours, the reaction was carried out, and then toluene was removed by an evaporator and a vacuum dryer to obtain a polymer [31].

-Examples 32 to 36-The polymers [30] and [31] obtained in Examples 30 and 31 were used to prepare gel coat resin compositions with the formulations and amounts shown in Table 13. To 100 parts of this gel coat resin composition, 2.5 parts of Aerosil # 200 (thixotropic agent, manufactured by Nippon Aerosil Co., Ltd.), 0.015 part as a metal component of cobalt naphthenate, 55% methyl ethyl ketone peroxide (Permeric N, Japan. Oil and fat company) 1.0
After mixing well was added parts, coating thickness 0 pneumatically 3.0 Kg / cm ² using a spray gun of the caliber 3.0 mm.
It was applied to a glass plate so as to have a thickness of 2 to 0.3 mm. Next, this was cured at 60 ° C. for 2 hours, then allowed to cool to room temperature, and a glass fiber reinforced plastic layer was molded and cured using an unsaturated polyester resin and glass fiber on the obtained coating film. Then, the molded product was released from the glass plate to obtain a molded product having a gel coat resin layer.

The coating film physical properties and weather resistance of the gel coat layer of this molded product were measured as follows, and the results are shown in Table 13.
Summarized in. The gel coat resin composition of the present invention has no sagging when applied to various molded products, and not only has a low viscosity during work and good workability, but also has high hardness and forms a gel coat layer with good weather resistance. I found out that (1) Viscosity, thixotropic degree and gel time The measurement was carried out according to JIS 6901 liquid unsaturated polyester resin test method. (2) Film-forming property The appearance (repellency) during spray coating was visually judged. (3) Pencil hardness A Mitsubishi Uni-Pencil was used to perform the test according to JIS K-5400. (4) Weather resistance (blister generation time) Using a Sunshine Weatherometer manufactured by Suga Test Instruments Co., Ltd., a sample molding was prepared under the conditions of an atmospheric temperature of 65 ° C., a spray cycle of 18 minutes / 120 minutes, and a light source of arc carbon.
Gloss of surface gel coat layer (000 hours)
Gloss) retention rate was shown.

Example 37 The polyurethane [15] obtained in Example 15 was subjected to the following evaluation tests. The results are shown in Table 15 below. (1) Tensile Elongation Test Using a No. 3 dumbbell, the tensile elongation test was performed according to JIS-K-6301. (2) Weather resistance test In a sunshine weather meter, a dumbbell formed by melting and casting at 200 ° C. was allowed to stand still under the conditions of an atmospheric temperature of 63 ° C., UV irradiation, 1 cycle for 2 hours, and 1 cycle for 18 minutes of rainfall. , After 24 hours and 330
Take out the dumbbell after a while and store its elongation (%)
Was measured. The elongation retention rate is in accordance with JISK6301
The tensile breaking elongation was measured and determined by the ratio before and after the weather resistance test.

The crosslinked film using the polyurethane of the present invention not only has a large elongation in a normal state, but is also excellent in strength and weather resistance. -Comparative Example 15-In Example 37, the same operation as in Example 37 was repeated except that the polymer shown in Table 15 below was used instead of the polyurethane [16] obtained in Example 16, and an evaluation test was performed. The results are shown in Table 15 below.

-Example 38- In Example 37, the same evaluation was carried out by using polyester [21] in place of the polyurethane [15] obtained in Example 15. The obtained results are shown in Table 16 below.
The crosslinked film using the polyester of the present invention not only has a large elongation in a normal state, but also has excellent strength and weather resistance.

Comparative Example 16 In Example 38, the same operation as in Example 38 was repeated except that the polymer shown in Table 16 below was used instead of the polyester [21] obtained in Example 21, and an evaluation test was conducted. went. The results are shown in Table 16 below. -Example 39- (Synthesis of polymer B having a polymerizable unsaturated group) Example 30
In the above, the same operation as in Example 30 was repeated except that 190 parts of the polymer [1] was used instead of 100 parts of the polymer [13] to obtain a polymer [39].

-Example 40- (Synthesis of polymer B having a polymerizable unsaturated group) Example 30
In, the same operation as in Example 30 was repeated except that 288 parts of the polymer [1] was used instead of 100 parts of the polymer [13] to obtain a polymer [40]. -Example 41- (Synthesis of polymer B having a polymerizable unsaturated group) Example 30
In, the same operation as in Example 30 was repeated except that 102 parts of the polymer [10] was used instead of 100 parts of the polymer [13] to obtain a polymer [41].

-Example 42- (Synthesis of Polymer B Having a Polymerizable Unsaturated Group) Example 30
In, the same operation as in Example 30 was repeated except that 73 parts of the polymer [5] was used instead of 100 parts of the polymer [13] to obtain a polymer [42]. —Example 43— 50 parts of the polymer [40] obtained in Example 40, 48.5 parts of styrene, a silane coupling agent (KBM-503,
1.5 parts of Shin-Etsu Chemical Co., Ltd. was mixed to obtain a resin composition.

Next, 200 parts of aluminum hydroxide (Hijilite H-320, average particle size 3.5 μm, Showa Denko KK) was kneaded into this resin composition using a high speed stirrer, and then, 0.8 part of Kayaester O (t-butylperoxy-2-ethylhexanoate, manufactured by Kayaku Nouri Co., Ltd.) was added as a curing agent, mixed and degassed under reduced pressure to obtain a blend. The viscosity of this formulation was 7 poise at a liquid temperature of 30 ° C.

This composition was poured into a 1000.times.600.times.6 mm casting mold and cured at 60.degree. C., which was cured in 30 minutes and then post-cured at 120.degree. C. for 2 hours.
The obtained cured product has a milky white, marble-like appearance that scatters light beautifully, has flame retardancy, and has excellent impact resistance and machinability as shown in Table 18. Met.

-Examples 44 to 47-Cured products were obtained by performing the same operations as in Example 43 except that the composition was as shown in Table 17. These cured products are
The milky white light was scattered and had flame retardancy, and as shown in Table 18, was excellent in impact resistance and machinability. -Comparative Example 17- 27 parts of polymethylmethacrylate (Acrypet MD011, manufactured by Mitsubishi Rayon Co., Ltd.) was added with methylmethacrylate 73
To obtain a methyl methacrylate syrup (resin solution) having a viscosity of 5 poise.

Next, aluminum hydroxide (Hidiglite H-320, average particle size 3.5 μm,
200 parts of Showa Denko KK was kneaded using a high-speed stirrer, then 0.8 parts of Kayaester O (made by Kayaku Nouri Co., Ltd.) was added as a curing agent, and after mixing, degassing was performed under reduced pressure. ,
A comparative resin formulation was obtained. The viscosity of this resin formulation was 200 poise at a liquid temperature of 30 ° C., and many bubbles remained,
And because of poor liquidity, casting was difficult. This resin composition was poured into a casting mold of 1000 × 600 × 6 mm and cured at 60 ° C., it was cured in 20 minutes and post-cured at 110 ° C. for 2 hours.

As to the physical properties of the obtained cured product, as shown in Table 20, there was a problem in impact resistance. -Comparative Example 18-As shown in Table 19, the same operation as in Example 43 was performed except that 20 parts of ethylene glycol dimethacrylate was used instead of 50 parts of the polymer [40] having a polymerizable unsaturated group. A cured product was obtained.

The physical properties of the obtained cured product are as shown in Table 20, and the impact resistance and workability were poor. -Comparative Example 19-Trimethylolpropane trimethacrylate 30 parts, styrene 50 parts, methyl methacrylate 20 parts and silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)
1.5 parts were mixed to obtain a monomer mixture.

Next, aluminum hydroxide (Hydileite H-320, average particle size 3.5 μm,
300 parts of Showa Denko KK was kneaded using a high-speed stirrer, and then Kayaester P-70 (t- was used as a curing agent.
Butyl peroxypivalate, Kayaku Nouri Co., Ltd.
0.5 parts by weight was added, mixed and then degassed under reduced pressure to obtain a comparative formulation. The viscosity of this formulation was 10 poise at a liquid temperature of 30 ° C.

This formulation is then added to 1000 × 600 × 6.
When poured into a casting mold of mm and cured at 50 ° C,
It was cured in 45 minutes and post-cured at 120 ° C. for 2 hours. The obtained cured product has a milky white, marble-like translucency that scatters light beautifully, and has flame retardancy.
As shown in Table 20, the heat distortion temperature was as high as 230 ° C., but the impact resistance and workability were poor.

Comparative Example 20 Vinyl ester resin (55 parts of bisphenol A type epoxy acrylate resin dissolved in 45 parts of styrene)
Aluminum hydroxide (Hidilite H-320, average particle size: 3.) in a resin solution prepared by mixing 1.5 parts of a silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) with 100 parts.
200 parts of 5 micron, manufactured by Showa Denko KK were kneaded using a high-speed stirrer, and then Kayaester O was used as a curing agent.
0.8 part (manufactured by Kayaku Nouri Co., Ltd.) was added, mixed and then degassed under reduced pressure to obtain a resin formulation for comparison.

The viscosity of this resin composition was 3 at a liquid temperature of 30 ° C.
Since it was 00 poise, many bubbles remained, and the fluidity was poor, which made casting difficult. 1 of this resin blend
When the mixture was poured into a casting mold of 000 × 600 × 6 mm and cured at 60 ° C., it was cured in 50 minutes and further post-cured at 110 ° C. for 2 hours. Table 20 shows the physical properties of the obtained cured product.
As shown in, there was a problem in impact resistance and workability.

Example 48 (Synthesis of Polymer C Having Carboxyl Group) 100 parts of the polymer [1] obtained in Example 1 and anhydrous were placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. Maleic acid 2.7
And 2.8 parts of triethylamine were charged and stirred at 80 ° C. for 6 hours to obtain a polymer [48].

With respect to the physical properties of the polymer [48], the number average molecular weight (Mn) was 15,000 as measured by GPC, and the number of terminal carboxyl groups (Fn (COOH)) was 4.2 based on the titration with alcoholic KOH and the above number average molecular weight. From this, it is considered that the reaction proceeded quantitatively. -Example 49- (Synthesis of Polymer C Having Carboxyl Group) The polymer obtained in Example 9 was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer.

[9] 100 parts, succinic anhydride 5.9
Parts and sodium acetate part 2.1 were charged and stirred at 80 ° C. for 6 hours to obtain a polymer [49].

With respect to the physical properties of the polymer [49], the number average molecular weight (Mn) is 5000 as measured by GPC, and the number of terminal carboxyl groups (Fn (COOH)) is 5.9 as determined by titration with an alcoholic KOH and the above number average molecular weight. From this, it is considered that the reaction proceeded quantitatively. -Example 50- (Synthesis | combination of the polymer C which has a carboxyl group) Example 14 was equipped with the stirrer, the reflux condenser, and the thermometer.
100 parts of the polymer [14] obtained in 1., phthalic anhydride 6.
Charge 3 parts and 2.0 parts of triethylamine, and add 6 parts at 80 ° C.
After stirring for a time, a polymer [50] was obtained.

With respect to the physical properties of the polymer [50], the number average molecular weight (Mn) was 23000 as measured by GPC, and the number of terminal carboxyl groups (Fn (COOH)) was 9.9 based on the titration with alcoholic KOH and the above number average molecular weight. From this, it is considered that the reaction proceeded quantitatively. -Example 51- (Synthesis of Polymer C Having Carboxyl Group) 100 parts of the polymer [8] obtained in Example 8 and itaconic anhydride 2 were placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. .7
Parts and 0.3 parts of triethylamine were charged and stirred at 90 ° C. for 6 hours to obtain a polymer [51].

The physical properties of the polymer [73] are as follows: number average molecular weight (Mn) is 16000 as measured by GPC, polymer 1 is determined by titration with alcoholic KOH and the above number average molecular weight.
The number of carboxyl groups (Fn (COOH)) per molecule is 8.5, which suggests that the reaction proceeded quantitatively. -Example 52-The polymer [48] obtained in Example 48 was mixed with the epoxy resin and the curing agent in the ratios shown in Table 21 to obtain an epoxy resin composition.

An adhesion test and a heat resistance test were conducted on this epoxy resin composition. The adhesion test, as an adherend,
A cold-rolled steel sheet with a thickness of 1.5 mm (0.5 mm for T-type peel test) was polished with # 100 sandpaper, washed and degreased with acetone, and heated at 150 ° C for 1 hour to cure the adhesive. Then, the tensile shearing force and the T-type peel strength were measured. The heat resistance test was carried out by leaving the sample of the adhesion test under hot air drying at 120 ° C. for about 6 days, and performing the adhesion test before and after the hot air drying to obtain the strength retention rate. The results are shown in Table 21.

Example 53 The same operation as in Example 52 was repeated, except that the polymer [48] obtained in Example 48 and the epoxy resin were preheated at 150 ° C. for 3 hours and then mixed with a curing agent. Then, an adhesion test and a heat resistance test were performed. The results are shown in Table 21. -Comparative Example 21- In Example 52, the adhesion test was performed by repeating the same operation as in Example 52 without using the polymer [48] as the rubber component. The results are shown in Table 21.

-Comparative Example 22-In Example 52, Hiker CTBN 130 manufactured by Ube Industries, Ltd. was used as a rubber component instead of using the polymer [48].
The same operation as in Example 52 was repeated except that 0X8 was used to perform an adhesion test and a heat resistance test. The results are shown in Table 21. -Comparative Example 23-In Example 53, instead of using the polymer [48], Hiker CTBN 130 manufactured by Ube Industries as a rubber component.
The same operation as in Example 53 was repeated except that 0X8 was used to perform an adhesion test and a heat resistance test. The results are shown in Table 21.

[0176]

[Table 1]

[0177]

[Table 2]

[0178]

[Table 3]

[0179]

[Table 4]

In Tables 1 to 4, "↑" represents the same as the immediately above column.

[0181]

[Table 5]

[0182]

[Table 6]

The annotations in Table 6 are as follows. * 1: Calculated from the nonvolatile content of the polymerization solution after completion of polymerization. * 2: In Examples 1, 11, and 23, measurement was performed by VPO, and in other Examples, measurement was performed by GPC using a calibration curve based on standard polystyrene. * 3: The average number of terminal hydroxyl groups (Fn (OH)) is JIS-
It was calculated based on the OH value determined according to K-1557 and the value of the number average molecular weight measured in * 2 above. * 4: First, the obtained polymer and Sumidule N-75
(Trifunctional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was mixed so that the molar ratio of the isocyanate group and the hydroxyl group was 1.1 / 1 to prepare a toluene solution of about 40%, and then dibutyl as a catalyst. A small amount of tin dilaurate was added and mixed well with stirring, and the mixture was reacted at 80 ° C. for 3 hours to obtain a polyurethane film. Next, after the film was sufficiently dried, it was subjected to Soxhlet extraction using tetrahydrofuran as a solvent for 8 hours, and the weight% of the insoluble matter remaining without being extracted was expressed as a gel fraction A. * 5: First, the obtained polymer and desmodul H (2
Functional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd., and the molar ratio of isocyanate group to hydroxyl group is 1.0.
After mixing 5/1 to make a toluene solution of about 40%, a small amount of dibutyltin dilaurate as a catalyst was added, and the mixture was stirred well and allowed to react at 80 ° C. for 3 hours to give a polyurethane film. Obtained.

Next, after sufficiently drying the film,
8 for Soxhlet extraction using tetrahydrofuran as a solvent
The weight percentage of the insoluble matter remaining without extraction over time was expressed as the gel fraction B.

[0185]

[Table 7]

[0186]

[Table 8]

The notes in Table 8 are as follows: * 1: Calculated from the nonvolatile content of the polymerization solution after completion of polymerization. * 2: Measured by GPC using a standard polystyrene calibration curve. * 3: The average number of terminal hydroxyl groups (Fn (OH)) is JIS-
It was calculated based on the OH value determined according to K-1557 and the value of the number average molecular weight measured in * 2 above. * 4: First, the obtained polymer and Sumidule N-75
(Trifunctional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was mixed so that the molar ratio of the isocyanate group and the hydroxyl group was 1.1 / 1 to prepare a toluene solution of about 40%, and then dibutyl as a catalyst. A small amount of tin dilaurate was added and mixed well with stirring, and the mixture was reacted at 80 ° C. for 3 hours to obtain a polyurethane film. Next, after the film was sufficiently dried, it was subjected to Soxhlet extraction using tetrahydrofuran as a solvent for 8 hours, and the weight% of the insoluble matter remaining without being extracted was expressed as a gel fraction A. * 5: First, the obtained polymer and desmodul H (2
Functional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd., and the molar ratio of isocyanate group to hydroxyl group is 1.0.
After mixing 5/1 to make a toluene solution of about 40%, a small amount of dibutyltin dilaurate as a catalyst was added, and the mixture was stirred well and allowed to react at 80 ° C. for 3 hours to give a polyurethane film. Obtained.

Next, after the film was sufficiently dried,
8 for Soxhlet extraction using tetrahydrofuran as a solvent
The weight percentage of the insoluble matter remaining without extraction over time was expressed as the gel fraction B.

[0189]

[Table 9]

[0190]

[Table 10]

[0191]

[Table 11]

[0192]

[Table 12]

[0193]

[Table 13]

[0194]

[Table 14]

[0195]

[Table 15]

[0196]

[Table 16]

[0197]

[Table 17]

[0198]

[Table 18]

[0199]

[Table 19]

[0200]

[Table 20]

[0201]

[Table 21]

[0202]

INDUSTRIAL APPLICABILITY In the production method of the present invention, a vinyl monomer (a), an alcohol (b) containing a polyfunctional alcohol as an essential component, and an initiator system (c) containing a hydrogen peroxide as an essential component in the reactor. It is possible to easily and surely introduce hydroxyl groups at both ends of the polymer and to easily and surely introduce at least two hydroxyl groups into at least one end by substantially not containing components other than). I have to. As a result, a polymer A having hydroxyl groups at both ends and at least two hydroxyl groups at at least one end is
It becomes possible to obtain easily and inexpensively and efficiently from a wide range of vinyl monomers including polar vinyl monomers.

The polymer A obtained by this production method is
By having hydroxyl groups at both ends and at least two hydroxyl groups at at least one end, various resins such as polyester resin, polyurethane resin, polycarbonate resin, etc., various block polymers, paints, and elastic wall materials can be obtained. , Waterproof film, adhesive, flooring, tackifier, adhesive, binder (magnetic recording medium, ink binder, casting binder, fired brick binder, graft material, microcapsule, glass fiber sizing, etc.), sealing material , Urethane foam (hard, semi-hard, soft), urethane RIM, UV / EB curable resin, high solid paint, thermosetting elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant , Gel coating agent, artificial marble resin, artificial marble impact resistance-imparting agent, Resins for films, films (laminate adhesives, protective films, etc.), resins for laminated glass, reactive diluents, various molding materials, elastic fibers, artificial leather, synthetic leather, etc., as well as various resin additives and their It is very useful as a raw material and the like, and by reacting hydroxyl groups at both ends by an appropriate method, functional groups other than hydroxyl groups (for example, polymerizable unsaturated groups such as vinyl groups, formyl groups, amino groups, and carboxyl groups). Group, ethynyl group, epoxy group, silanol group, alkoxysilyl group,
Hydrosilyl group, mercapto group, oxazoline group, maleimide group, azlactone group, lactone group, bromine, chlorine, etc.) at both ends, and at least one terminal has at least two functional groups other than hydroxyl group to a polymer It can be converted easily. This polymer is also very useful. For example, having a carboxyl group at both ends, and
At least two carboxyl groups on at least one end
The individual polymer (polymer C of the present invention) is very effective as an impact resistance imparting agent for an epoxy adhesive. Further, by adding a plurality of ethylene oxides or propylene oxides to the terminal hydroxyl group of the polymer A, a raw material such as a surfactant can be obtained.

A composition of the present invention containing as an essential component a polymer A obtained by the production method of the present invention and a polyfunctional compound (d) having two or more functional groups capable of reacting with a hydroxyl group in one molecule. Are various resins such as polyester resin, polyurethane resin, polycarbonate resin, various block polymers, paints, elastic wall materials, coating waterproof materials, adhesives, floor materials, tackifiers, adhesives, binders (magnetic recording media, Ink binder, casting binder, baked brick binder, graft material, microcapsule, glass fiber sizing, etc.), sealing material, urethane foam (hard, semi-hard, soft), urethane RIM, UV / E
B-curing resin, high solid coating, thermosetting elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coating agent, artificial marble resin, artificial marble impact resistance-imparting agent , Resin for ink,
Used as raw materials for films (laminate adhesives, protective films, etc.), laminated glass resins, reactive diluents, various molding materials, elastic fibers, artificial leather, synthetic leather, etc., as well as various resin additives and their raw materials, etc. In addition to having flexible and tough mechanical properties, depending on the type of the monomer component (b) that constitutes the main chain of the polymer A, very good transparency, weather resistance, water resistance, and Physical properties such as hydrolysis resistance and chemical resistance are fully exhibited, and very good physical properties are exhibited.

For example, as the polymer A, a low molecular weight polymer having a weight average molecular weight of about 1000 to 10000 is used, which is combined with a bifunctional isocyanate compound or the like to be coated on a base material and then chain-extended to give an adhesive property. When used as an agent, when a conventional polymer obtained by copolymerizing a vinyl-based monomer having a functional group is used (usually, one having a weight average molecular weight of 100,000 or more is used)
Compared with the above, the viscosity of the pressure-sensitive adhesive composition is low, so that the amount of solvent used can be reduced and the workability is improved. A composition is obtained.

When the composition of the present invention is used for an adhesive composition, since the composition contains the polymer A as one of the essential components, it contains a vinyl-based monomer having a functional group. Compared with the case of using an acrylic polymer obtained by polymerization, when the same adhesive performance is obtained, the viscosity of the adhesive composition is low, so that the amount of solvent used can be reduced and workability is good. As described above, it is possible to obtain an effect that the conventional adhesive composition does not have. In addition, the adhesive using the composition of the present invention has excellent heat resistance as compared with the adhesive using the polyether polyol currently used, and the adhesive using the polyester polyol currently used. Hydrolysis resistance is superior to that of

When the composition of the present invention is used for urethane foam, since the polymer A is used in combination with a conventionally known isocyanate compound or the like, flexibility, weather resistance, heat resistance, water resistance, chemical resistance, and resilience are obtained. In the elastic modulus, an effect not obtained by the conventional urethane foam composition can be obtained. Further, the urethane foam using the composition of the present invention has excellent heat resistance as compared with the urethane foam using the polyether polyol currently used, and the urethane foam using the polyester polyol currently used. Hydrolysis resistance is excellent by comparison.

When the composition of the present invention is used for a sealing material, by combining the polymer A with a conventionally known isocyanate compound or the like, it is flexible and tough, and has weather resistance, heat resistance, water resistance, chemical resistance, In terms of impact resilience, an effect not obtained by the conventional sealing material composition can be obtained.
Further, the sealing material using the composition of the present invention is superior in heat resistance to the sealing material using the polyether polyol which is currently used.

The present invention obtained by reacting the polymer A with a compound (h) having two kinds of reactive groups of a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group in one molecule. In addition to the polymer B, the composition containing a vinyl monomer having at least one polymerizable unsaturated group in one molecule as an essential component is a gel coat resin composition, a resin composition for artificial marble, and a laminated glass. When used in a resin composition or the like, a reaction shrinkage during molding is small, a viscosity during work is low, workability is good, and a cured product has a large hardness, is tough, and has good weather resistance.

The artificial marble obtained from the above-mentioned resin composition for artificial marble is excellent in heat resistance and weather resistance, and by using the polymer B of the present invention, the composition has a small shrinkage due to polymerization during molding. Therefore, problems such as cracking during molding can be solved. Further, since it is incorporated into the crosslinked structure at the terminal of the polymer, by using a rubber component in the polymer main chain, the flexibility of the molded product is greatly improved, and a molded product with extremely good impact resistance is obtained. You can Also, for the same reason, there is no chipping during cutting and the machinability is good.

Further, in order to suppress the polymerization shrinkage at the time of polymerization and impart flexibility to the molded product, unlike the conventional case where a thermoplastic polymer having no polymerizable unsaturated group is added, Since the polymer to be prepared has a polymerizable unsaturated group at both ends and at least two polymerizable unsaturated groups at at least one end, it is incorporated into the crosslinked structure even after molding, so the amount of addition is increased. However, the heat resistance is not deteriorated, and flexibility is sufficiently imparted.

The polyurethane of the present invention obtained by reacting the polymer A with the polyfunctional isocyanate compound (e), and the compound (g) containing the polymer A having two or more carboxyl groups in one molecule. When used as a molding material, the polyester of the present invention obtained by reacting with is not only flexible and tough mechanical properties but also a vinyl-based monomer component (b) constituting the main chain of the polymer A. Depending on the type, very good transparency, weather resistance, water resistance, hydrolysis resistance, oil resistance, chemical resistance and other physical properties are fully exhibited, and very useful physical properties Is.

According to the present invention, it has a carboxyl group at both ends, and at least one end has at least 2
The polymer C having a number of carboxyl groups has the same transparency as the polymer A having a hydroxyl group by arbitrarily selecting the type of the vinyl-based monomer (b) constituting the main chain.
It has weather resistance, water resistance, hydrolysis resistance, chemical resistance, and various resins such as polyester derived from the polymer C are very stretchable (having good bending workability) and tough. Since it exhibits such characteristics, paints, adhesives, various molding materials, resin modifiers (impact resistance imparting materials), damping materials, elastic wall materials, floor materials, fiber processing materials, UV / EB curing It is useful as a raw material for resins and the like. Further, this polymer C has a feature that it can be used as a curing agent and an additive for an epoxy resin which has been difficult to use at the terminal of a hydroxyl group.

Next, a resin composition containing as an essential component the polymer C according to the present invention and a compound (l) having two or more functional groups capable of reacting with a carboxyl group in one molecule. Is transparent, weather resistant, water resistant, and hydrolysis resistant like the composition containing the polymer A by arbitrarily selecting the type of the vinyl-based monomer (b) constituting the main chain. Various resins such as polyester having chemical resistance, and derived from a composition containing the polymer C exhibit properties of being extremely stretchable (having good bending workability) and being tough. Useful as a raw material for paints, adhesives, various molding materials, resin modifiers (impact resistance imparting materials), damping materials, elastic wall materials, floor materials, fiber processing materials, UV / EB curing resins, etc. It is something. Further, the composition containing the polymer C is characterized in that it can be used for an epoxy resin composition which has been difficult to use at a hydroxyl group terminal.

In the epoxy resin composition containing the polymer C of the present invention as an essential component, addition of the polymer C as a rubber component to the epoxy resin improves the toughness, heat resistance and weather resistance. In terms of properties, an effect not obtained by the conventional epoxy resin composition can be obtained. That is, the epoxy resin composition using the polymer C of the present invention is excellent in heat resistance and weather resistance as compared with the epoxy resin compositions to which polybutadiene polyol and polybutadiene / acrylonitrile polyol which are currently used are added.

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[Procedure amendment] [Date of submission] November 1, 1993 [Procedure amendment 1] [Document name for amendment] Specification [Item name for amendment] [Correction method] Change [Correction content] [0032] Multifunctional The alcohol can be used in the reaction system as an aqueous solution. In this case, the concentration of the aqueous solution is not particularly limited, but the concentration of the polyfunctional alcohol aqueous solution is preferably 50% by weight or more in view of controlling the molecular weight of the polymer and controlling the reaction temperature. When the viscosity during polymerization is low
Since the homogeneity of the system is increased, the alcohols (b) will be described later.
Ethylene glycol and bishydride used in the examples
Roxyethyl sulfone, propylene glycol, 1,4
-Butanediol, glycerol, trimethylol pro
Bread, sorbitol, butanol, pentaerythritol
Low molecular weight substances such as glucose and glucose
Preferably has a molecular weight of 400 or less, and has a molecular weight of 2
Those of 00 or less are more preferable. Examples of the initiator system (c) containing hydrogen peroxide as an essential component used in the present invention include a case where a compound (k) capable of promoting polymerization by combination with hydrogen peroxide is used in combination with hydrogen peroxide, An example is when hydrogen peroxide is used alone. Hydrogen peroxide can be used as an industrially available aqueous solution, and the concentration thereof is not particularly limited. Examples of the compound (k) include a hydrogen peroxide decomposition catalyst, a reducing compound that performs a redox reaction with hydrogen peroxide, a surfactant, and the like. That is, the initiator system (c) that essentially requires hydrogen peroxide is hydrogen peroxide alone, or hydrogen peroxide is an essential component and is composed of a hydrogen peroxide decomposition catalyst, a reducing compound and a surfactant. It is a mixture containing one or more compounds selected from the group consisting of and capable of promoting polymerization. Hereinafter, the compound (k) capable of promoting the polymerization by combining with hydrogen peroxide will be specifically described. [Procedure Amendment 2] [Document name for amendment] Specification [Item name for amendment] [Correction method] Change [Details of amendment] The hydrogen peroxide decomposition catalyst used in the present invention is not particularly limited, For example, metal halides such as lithium chloride and lithium bromide; solid acids such as titanium oxide and silicon dioxide; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, hydrobromic acid and metal salts thereof; benzenesulfonic acid. , Alkylbenzenesulfonic acid such as p-toluenesulfonic acid and metal salts thereof; carboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, isolacic acid and benzoic acid and metal salts and esters thereof; pyridine, indole and its derivatives, imidazole And heterocyclic amines such as carbazole and its derivatives, and the like. [Procedure Amendment 3] [Name of Documents to Amend] Specification [Name of Item to Amend] 0037 [Correction Method] Change [Details of Amendment] In the production method of the present invention, during the reaction, the vinyl-based unit Substantially no components other than the monomer (a), alcohols (b) requiring polyfunctional alcohol and initiator system (c) requiring hydrogen peroxide are used. Specifically, the components other than the vinyl-based monomer (a), the alcohols (b) that require a polyfunctional alcohol, and the initiator system (c) that requires hydrogen peroxide are 10% by weight of the whole.
It should be below. Then, (a), (b),
The components other than (c) are preferably 5% by weight or less, and most preferably, the components other than (a), (b) and (c) are not contained at all. (A), (b), (c)
10% by weight or less of the components other than the above with respect to the total amount of the components in the reactor.
If used even at lower levels, it will introduce hydroxyl groups at the ends.
Probability may decrease. However, this (a),
Components other than (b) and (c) relative to the total amount of components in the reactor
By adding about 10% by weight or less, the viscosity in the system
It is preferable for manufacturing operations such as heat removal by latent heat of vaporization.
The effect may be obtained. [Procedure Amendment 4] [Name of Documents to Amend] Specification [Name of Items to Amend] 0101 [Correction Method] Change [Details of Amendment] [0101] Subsequently, this polymer is contained using an extraction solvent of toluene / water system. The polymer was extracted and separated from the reaction mixture to obtain a toluene solution containing the polymer. Toluene was distilled off, and the residue was dried at 45 ° C. under reduced pressure to obtain a purified polymer [1]. The number average molecular weight (Mn) of the purified polymer [1] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and was 15,000. The average number of terminal hydroxyl groups (Fn (OH)) of the polymer [1] is JIS-K-1.
Based on the OH value determined according to 557 and the value of the number average molecular weight measured above, the result was 3.3 (mol / polymer 1 mol). In addition, the polymer [1] after purification contains
Corrected from the measurement of residual amount of ethylene glycol
The average number of terminal hydroxyl groups (Fn (OH)) of the polymer [1] is
It was 2.6 (mol / polymer 1 mol). [Procedure Amendment 5] [Document name for amendment] Specification [Item name for amendment] 0103 [Correction method] Change [Details of amendment] Number average molecular weight of polymer [2] after purification (M
n) was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC) . Also, J I
Polymerization after purification of the OH value determined according to SK-1557
Measurement of residual amount of alcohols (b) contained in body [2]
The average number of terminal hydroxyl groups (Fn (OH)) was calculated based on the OH value corrected from the constant and the value of the number average molecular weight measured above. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1. [Procedure Amendment 6] [Name of document to be amended] Specification [Name of item to be amended] 0104 [Correction method] Change [Details of amendment] -Example 3-Agitator, nitrogen introduction tube, thermometer and reflux cooling tube 67 parts of ethylene glycol was charged into the flask provided, the inside of the flask was replaced with nitrogen, and then the temperature was raised to 140 ° C. while gently blowing nitrogen gas. After the temperature in the reaction vessel became stable, a mixture of 60 parts of butyl acrylate and 40 parts of methyl methacrylate dissolved with 1.7 parts of dodecylbenzene sulfonic acid, 3.6 parts of 60% hydrogen peroxide solution and ethylene. After the mixture with 33 parts of glycol was added dropwise over 1 hour, stirring was continued at 140 ° C. for 10 minutes to complete the polymerization. Then, a purified polymer [3] was obtained by the same purification method as in Example 1. [Procedure Amendment 7] [Document name for amendment] Specification [Item name for amendment] 0105 [Correction method] Change [Details of amendment] [0105] Number average molecular weight (M) of polymer [3] after purification
n) was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC) . Also, J I
Polymerization after purification of the OH value determined according to SK-1557
Measurement of residual amount of alcohols (b) contained in body [3]
The average number of terminal hydroxyl groups (Fn (OH)) was calculated based on the OH value corrected from the constant and the value of the number average molecular weight measured above. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1. [Procedure Amendment 8] [Name of Document to Amend] Specification [Name of Item to Amend] 0106 [Correction Method] Change [Details of Amendment] -Example 4-Types of vinyl monomers and alcohols are shown in the table below. The polymerization reaction was performed in the same manner as in Example 3 except that the changes were made as described in 1. Then, a purified polymer [4] was obtained by the same purification method as in Example 1. The number average molecular weight (Mn) of the purified polymer [4] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC) . Further, the OH value determined according to JIS-K-1557 is an alcohol contained in the purified polymer [4].
Average number of terminal hydroxyl groups based on the OH value corrected from the measurement of the residual amount of the polyols (b) and the value of the number average molecular weight measured above.
(Fn (OH)) was calculated. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1. [Procedure Amendment 9] [Name of Document to Amend] Specification [Name of Item to Amend] 0108 [Correction Method] Change [Details of Correction] [0108] Number average molecular weight (Mn) of the polymer [5] to [7] after purification ), Gel permeation chromatography (GP
It was measured by the standard polystyrene conversion method using C) .
In addition, the OH value determined according to JIS-K-1557 should be
Alcohols contained in polymers [5] to [7] after production
OH number corrected from the measurement of the remaining amount in (b) and measured above
The average number of terminal hydroxyl groups (Fn
(OH)) was calculated. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1. [Procedure Amendment 10] [Name of Document to Amend] Specification [Name of Item to Amend] 0110 [Correction Method] Change [Details of Correction] [0110] Number average molecular weight of polymer [8] after purification (M
n) was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC) . Also, J I
Polymerization after purification of the OH value determined according to SK-1557
Measurement of residual amount of alcohols (b) contained in body [8]
The average number of terminal hydroxyl groups (Fn (OH)) was calculated based on the OH value corrected from the constant and the value of the number average molecular weight measured above. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1. [Procedure Amendment 11] [Document name for amendment] Specification [Name of item for amendment] 0112 [Correction method] Change [Details of amendment] [0112] Number average molecular weight (Mn) of the polymer [9] and [10] after purification ), Gel permeation chromatography (GP
It was measured by the standard polystyrene conversion method using C) .
In addition, the OH value determined according to JIS-K-1557 should be
Alcohol contained in polymers [9] and [10] after production
Based on the OH value corrected from the measurement of the residual amount of the group (b) and the value of the number average molecular weight measured above, the average number of terminal hydroxyl groups (F
n (OH)) was calculated. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1. [Procedure Amendment 12] [Name of Documents to Amend] Specification [Name of Items to Amend] 0114 [Correction Method] Change [Details of Correction] [0114] The number average molecular weight (Mn) of the purified polymer [11] is determined by gel It was measured by a standard polystyrene conversion method using permeation chromatography (GPC) . Also,
The OH value determined according to JIS-K-1557 after purification
Remaining alcohols (b) contained in the polymer [11]
The average number of terminal hydroxyl groups (Fn (OH)) was calculated based on the OH value corrected from the measurement of the amount and the value of the number average molecular weight measured above. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1. [Procedure Amendment 13] [Document name for amendment] Specification [Name of item for amendment] 0116 [Correction method] Change [Details of amendment] [0116] Number average molecular weight (Mn of polymer [12] to [14] after purification ) By gel permeation chromatography (G
Measured by the standard polystyrene equivalent method using a PC)
It was In addition, the OH value determined according to JIS-K-1557
Of the polymer contained in the polymers [12] to [14] after purification
The average terminal hydroxyl group based on the OH value corrected from the measurement of the residual amount of the call (b) and the value of the number average molecular weight measured above.
The number (Fn (OH)) was calculated. The results are shown in Table 6 below together with the polymerization rate obtained in the same manner as in Example 1. [Procedure Amendment 14] [Document name for amendment] Specification [Item name for amendment] 0119 [Correction method] Change [Details of amendment] Number average molecular weight and average terminal hydroxyl group of the obtained comparative polymer [2] Number (Fn (OH)) in Example 1
The number average molecular weight was 2,200 and the average number of terminal hydroxyl groups (Fn (OH)) was 0.3 . The results are shown in Table 8 below together with the polymerization rate obtained in the same manner as in Example 1. -Comparative Example 3- In Example 5, the types and ratios of the vinyl-based monomer (a), the alcohols (b) requiring the polyfunctional alcohol and the initiator system (c) requiring the hydrogen peroxide were determined as follows. Table 7 below
And (a), (b),
A comparative polymer [3] was obtained in the same manner as in Example 5 except that the mixture of 100 parts of (c) and 100 parts of toluene was continuously fed to the reactor. [Procedure Amendment 15] [Document Name for Amendment] Specification [Item Name for Amendment] 0178 [Correction Method] Change [Content of Amendment] [Table 3] [Procedure Amendment 16] [Name of document to be amended] Specification [Name of item to be amended] 0179 [Correction method] Change [Details of amendment] [Table 4] [Procedure Amendment 17] [Document Name to Amend] Specification [Name of Item to Amend] 0181 [Correction Method] Change [Details of Correction] [0181] [Table 5] [Procedure Amendment 18] [Document Name for Amendment] Specification [Item Name for Amendment] 0182 [Correction Method] Change [Correction Details] [0182] [Table 6] [Procedure Amendment 19] [Name of Documents to Amend] Specification [Name of Item to Amend] 0183 [Correction Method] Change [Details of Amendment] The annotations in Table 6 are as follows. ※ 1: was measured by GPC using the calibration curve by the standard polystyrene. * 2 : The average number of terminal hydroxyl groups (Fn (OH)) is JIS-
OH value determined according to K-1557 in the purified polymer
Corrected from the measurement of the residual amount of alcohols (b) contained in
It was calculated based on the OH value and the number average molecular weight value measured in * 1 above. * 3 : First, the obtained polymer and Sumidule N-75
(Trifunctional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was mixed in such a manner that the molar ratio of the isocyanate group and the hydroxyl group was 1.1 / 1 to make a toluene solution of about 40%, and then dibutyl was used as a catalyst. A small amount of tin dilaurate was added and mixed well with stirring, and the mixture was reacted at 80 ° C. for 3 hours to obtain a polyurethane film. Next, after the film was sufficiently dried, it was subjected to Soxhlet extraction using tetrahydrofuran as a solvent for 8 hours, and the weight% of the insoluble matter remaining without being extracted was expressed as a gel fraction A. * 4 : First, the obtained polymer and Desmodur H (2
Functional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd., and the molar ratio of isocyanate group to hydroxyl group is 1.0.
After mixing 5/1 to make a toluene solution of about 40%, a small amount of dibutyltin dilaurate as a catalyst was added, and the mixture was stirred well and allowed to react at 80 ° C. for 3 hours to give a polyurethane film. Obtained. [Procedure amendment 20] [Document name for amendment] Specification [Item name for amendment] 0185 [Amendment method] Change [Amendment content] [0185] [Table 7] [Procedure Amendment 21] [Name of Documents to Amend] Specification [Name of Items to Amend] 0186 [Correction Method] Change [Contents of Amendment] [Table 8] [Procedure Amendment 22] [Name of Documents to Amend] Specification [Name of Item to Amend] 0187 [Correction Method] Change [Details of Amendment] [0187] The notes in Table 8 are as follows. * 1 : Measured by GPC using a standard polystyrene calibration curve. * 2 : The average number of terminal hydroxyl groups (Fn (OH)) is JIS-
OH value determined according to K-1557 in the purified polymer
Corrected from the measurement of the residual amount of alcohols (b) contained in
It was calculated based on the OH value and the number average molecular weight value measured in * 1 above. * 3 : First, the obtained polymer and Sumidule N-75
(Trifunctional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was mixed in such a manner that the molar ratio of the isocyanate group and the hydroxyl group was 1.1 / 1 to make a toluene solution of about 40%, and then dibutyl was used as a catalyst. A small amount of tin dilaurate was added and mixed well with stirring, and the mixture was reacted at 80 ° C. for 3 hours to obtain a polyurethane film. Next, after the film was sufficiently dried, it was subjected to Soxhlet extraction using tetrahydrofuran as a solvent for 8 hours, and the weight% of the insoluble matter remaining without being extracted was expressed as a gel fraction A. * 4 : First, the obtained polymer and Desmodur H (2
Functional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd., and the molar ratio of isocyanate group to hydroxyl group is 1.0.
After mixing 5/1 to make a toluene solution of about 40%, a small amount of dibutyltin dilaurate as a catalyst was added, and the mixture was stirred well and allowed to react at 80 ° C. for 3 hours to give a polyurethane film. Obtained.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Reference number within the agency FI Technical display location C08G 63/12 NMD 7107-4J 85/00 NVC 8416-4J (72) Inventor Hiroyuki Ikeuchi Nishimitabi Suita City, Osaka Prefecture Town No. 5-8, Nippon Shokubai Central Research Laboratory (72) Inventor Fumihide Tamura No. 5, Nishimitabicho, Suita City, Osaka Prefecture Nihon Shokubai Central Research Laboratory

Claims (13)

[Claims] 1. The polymerization of a vinyl-based monomer (a) is carried out in the presence of an alcohol (b) containing a polyfunctional alcohol as an essential component.
A method carried out using an initiator system (c) which essentially requires hydrogen peroxide, comprising the steps of (a), (b),
A method for producing a polymer, which is substantially free of components other than (c). 2. The method for producing a polymer according to claim 1, wherein the polyfunctional alcohol contains carbon, hydrogen and oxygen as essential constituent elements and can further contain a nitrogen element. 3. The polyfunctional alcohol has a C═S bond, a C—
The method for producing a polymer according to claim 1, wherein the polymer has any one of S—C bond, SO ₂ bond and SO ₃ bond. 4. The initiator system (c) is hydrogen peroxide alone or is selected from a hydrogen peroxide decomposition catalyst, a reducing compound that performs a redox reaction with an initiator and a surfactant. The method for producing a polymer according to any one of claims 1 to 3, which is a mixture of one or more kinds of compounds and hydrogen peroxide. 5. The method for producing a polymer according to claim 1, wherein a tubular reactor is used as a reactor for carrying out the polymerization reaction. 6. The method for producing a polymer according to claim 1, wherein a kneader is used as a reactor for carrying out the polymerization reaction. 7. An essential component comprising a polymer obtained by the production method according to any one of claims 1 to 6 and a compound (d) having two or more functional groups capable of reacting with a hydroxyl group in one molecule. As a composition. 8. A polymer obtained by the method according to claim 1, wherein two molecules of two kinds of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group, are contained in one molecule. Obtained by reacting with the compound (h) also contained therein,
A polymer having a polymerizable unsaturated group. 9. A composition comprising, as an essential component, the polymer having a polymerizable unsaturated group according to claim 8 and a vinyl monomer having at least one polymerizable unsaturated group in one molecule. 10. A polymer obtained by the production method according to claim 1, wherein two reactive groups of a functional group capable of reacting with a hydroxyl group and a carboxyl group are combined in one molecule. A polymer having a carboxyl group, which is obtained by reacting with the compound (i) and / or an acid anhydride. 11. A polyfunctional compound having, in one molecule, two or more isocyanate groups, the polyol component (j) containing as an essential component the polymer obtained by the method according to any one of claims 1 to 6. Isocyanate compound (e)
Polyurethane obtained by reacting with. 12. A compound having two or more carboxyl groups in one molecule, comprising a polyol component (j) containing the polymer obtained by the production method according to any one of claims 1 to 6 as an essential component. Polyester obtained by reacting with g). 13. A block polymer comprising a polymer obtained by the production method according to any one of claims 1 to 6 as an essential component.