JPH09291104A - Composition comprising polymer having hydroxyl groups at both terminals, and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compsn. having good toughness, weatherability, water resistance, etc., and comprising a polymer having hydroxyl groups at both terminals and obtd. from a wide variety of vinyl monomers including a polar vinyl monomer such as (meth)acrylic acid or a (meth)acrylic ester; and a user thereof. SOLUTION: This compsn. comprises as the indispensable components (I) a polymer having hydroxyl groups at both terminals and (II) a compd. having at least 2 functional groups each reactive with a hydroxyl group per molecule. This polymer (I) is obtd. by polymerizing (b) a vinyl monomer in the presence of (a) a compd. of the formula: HO-A-(S)x -B-OH (wherein A and B are each a bivalent org. group; and x is an integer of 2 to 5) while using (c) a radical polymn. initiator. In this case, polymn. is effected in such a way that the molar amt. of the compd. (a) existing in a reactor is always at least 50mol times as much as that of the radical polymn. initiator (c) throughout the reaction, during which no other material is used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition containing a polymer having hydroxyl groups at both ends and its use.

[0002]

2. Description of the Related Art Paints, adhesives, urethane foams, sealing agents, gel coat materials, thermoplastic elastomers, various molding materials, resin modifiers (impact resistance imparting materials), vibration damping materials, elastic wall materials, floors. As a polymer having a hydroxyl group for use as a material such as a material, a fiber processing material, a UV / EB curing resin, a raw material for a reactive diluent for a high solid coating, a vinyl-based monomer having a hydroxyl group in a side chain is used. Examples include copolymers, polyethers having hydroxyl groups at the ends, polyesters, polybutadienes, and polycarbonates. However, these polymers have the following problems. First, a copolymer of a vinyl monomer having a hydroxyl group in a side chain is formed by random radical polymerization of a vinyl monomer having a hydroxyl group and a vinyl monomer having no hydroxyl group. It is difficult to suppress the by-product of the copolymer having no, and it is necessary to increase the hydroxyl group content in the copolymer in order to avoid this, and the number of hydroxyl groups in one molecule was varied. . Therefore, when reacted with a polyfunctional compound having reactivity with a hydroxyl group, an unreacted copolymer remains, the distance between reaction points varies widely, and a play chain that is not directly involved in the polymer structure after the reaction. For example, due to the formation of the above-mentioned portion or the remaining of a hydroxyl group which does not participate in the reaction, a polymer having sufficient elongation (good bending workability) and toughness cannot be obtained.

Next, polyethers, polyesters, polybutadienes, etc. having a hydroxyl group at the terminal have a hydroxyl group at the terminal, so that they have few drawbacks such as the copolymer of the vinyl monomer having a hydroxyl group in the side chain. , Because of the ether bond in the main chain in the case of polyether, the ester bond in the main chain in the case of polyester, and the unsaturated double bond in the main chain in the case of polybutadiene, weather resistance, water resistance, heat resistance, etc. Has the disadvantage of not being good.

As described above, at present, paints, tacky adhesives, urethane foams, sealing agents, gel coat materials, thermoplastic elastomers, various molding materials, resin modifiers (resisting materials containing a polymer having a hydroxyl group are used. Impact-imparting material), damping material, elastic wall material, floor material, fiber processing material, UV / EB curable resin, reactive diluent for high solid paint, etc., toughness, elongation (bending) At present, none of them satisfy all the required performances such as processability), weather resistance and water resistance.

As a method for producing a vinyl polymer having a hydroxyl group at the terminal, for example, 2-mercaptoethanol or the like is used as a chain transfer agent to introduce one hydroxyl group at one terminal of the polymer and 2-hydroxymethacrylic acid is used. There is a method of obtaining a polymer having a hydroxyl group at the terminal by introducing another hydroxyl group into the polymer molecule on average by copolymerization with ethyl or the like.

However, in this method, although an average of two hydroxyl groups is introduced per molecule of the polymer, only one of the average two hydroxyl groups is introduced into one end of the polymer, and One hydroxyl group is introduced not in the terminal but in the middle of the main chain. In addition, since another hydroxyl group is introduced by copolymerization, the total number of hydroxyl groups per polymer has a distribution (dispersion) such as one or more than one, and the number of hydroxyl groups is one. A wide distribution can be obtained for distance. Therefore, the obtained polymer hardly exhibits the advantages of a polymer having a hydroxyl group at both ends as described below. In addition, the addition of the mercaptan compound causes a problem that the polymerization is extremely slowed down, the polymerization rate is not increased, and the odor of the remaining mercaptan remains.

Apart from this, as a method for producing a vinyl polymer having hydroxyl groups at both ends, for example, as shown in the following (i) to (iii), the presence of various initiators and chain transfer agents, etc. There is a method of radically polymerizing a vinyl monomer below. (I) A method of obtaining a polymer having hydroxyl groups at both ends by polymerizing styrene or butadiene using an initiator having a hydroxyl group (see “J. Polym. Sc”).
i. , Part A1 ", Vol. 9, p. 2029, 19
(See the 71st edition).

(Ii) By a method of thermal polymerization or photopolymerization using a dithiocarbamate or thiuram disulfide having a hydroxyl group as an initiator, or by using the above dithiocarbamate or thiuram disulfide as a chain transfer agent and hydrogen peroxide or the like. A method of obtaining a polymer having hydroxyl groups at both ends by polymerizing using an initiator (see JP-A-61-271306).

(Iii) A method of obtaining a polymer having hydroxyl groups at both ends by polymerization using a disulfide or trisulfide having hydroxyl groups at both ends as a chain transfer agent (see JP-A-54-47782). However, the above-described conventional methods (i) to (iii) for producing a polymer having hydroxyl groups at both ends have their respective drawbacks as described below. It is not easy to synthesize a polymer having a hydroxyl group at the end reliably, inexpensively, conveniently and industrially.

First, in the method (i), usable vinyl monomers are limited to butadiene and styrene, and polar vinyl monomers such as acrylic acid esters and methacrylic acid esters cannot be used. There was a problem. In the method (ii), thiuram disulfide having a functional group such as a hydroxyl group is unstable, and therefore, it is difficult to handle them. Further, there is a problem that the produced polymer is colored yellow.

Finally, in the above method (iii), the ratio of the chain transfer agent to the initiator is not taken into consideration. There is a problem that the initiator segment enters the coalesced end and a polymer having a hydroxyl group only at one end is by-produced to form a polymer having a low number of terminal hydroxyl groups. As mentioned above, acrylic acid,
Methods for industrially producing polymers having hydroxyl groups at both ends from a wide range of vinyl monomers including polar vinyl monomers such as acrylic esters, methacrylic acids, and methacrylic esters have been established. There is no present.

Although an industrial manufacturing method has not been established,
The polymer having hydroxyl groups at both ends can be easily converted with other functional groups by reacting the hydroxyl groups at both ends with an appropriate method, and the reactivity of the hydroxyl groups at both ends can be improved. By utilizing these and reacting these hydroxyl groups by an appropriate method, they are linearized and / or reticulated, and as a result, a polymer compound having various good physical properties such as strength, heat resistance, weather resistance and durability is obtained. ..

This polymer having hydroxyl groups at both ends is
By exhibiting the feature of having hydroxyl groups at both ends, for example, there are the following significant advantages. When used as various resin raw materials such as polyester resin, polyurethane resin and polycarbonate resin, there is no unreacted substance which impairs the physical properties of the material, and all polymers are surely incorporated into the resin crosslinked structure.

A polymer in which a functional group is introduced into a side chain by copolymerizing a vinyl-based monomer having a functional group such as a hydroxyl group, a carboxyl group and an amino group (hereinafter referred to as a functional group-containing vinyl-based monomer copolymer). When a polymer is used for the reaction, the end thereof becomes a play part (free end) that is not incorporated in the resin (crosslinking) structure, but in a polymer having hydroxyl groups at both ends, Nothing happens.

Since the variation in the distance between the functional groups is extremely small as compared with the vinyl monomer copolymer containing a functional group, the distance between the reaction points (crosslinking points) becomes almost constant, and a uniform resin (crosslinking) structure is formed. to make. A functional group-containing vinyl monomer copolymer having an average number of functional groups of 2.0 was prepared.
Even if it is attempted to synthesize a thermoplastic polymer by reacting with a functional chain extender, most of it is thermoset because a polymer having three or more functional groups is included statistically because of the synthesis method. As a functional polymer, a thermoplastic polymer cannot be synthesized, but does not contain a polymer having three or more functions.
In the case of a polymer having hydroxyl groups at both ends, a chain-extended thermoplastic polymer can be easily synthesized.

A raw material such as a reactive diluent contains a polymer having hydroxyl groups at both ends, and various resins such as polyester resin, polyurethane resin, polycarbonate resin, paints, adhesives, sealing materials, urethane foams, gel coat materials. , Thermoplastic elastomer, molding material, resin modifier (impact resistance imparting material), damping material, elastic wall material, floor material, fiber processing material, UV / EB curable resin, high solid paint, etc. Further, various resin additives containing a polymer having hydroxyl groups at both ends are very useful, but it is further desired to improve toughness, weather resistance, water resistance and the like.

[0017]

[Means for Solving the Problems] In view of such 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, which can be easily and inexpensively and efficiently obtained at both terminals. An object of the present invention is to provide a composition containing a polymer having a hydroxyl group and having good toughness, weather resistance, water resistance and the like, and its use.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION In order to solve the above problems, a composition containing a polymer having hydroxyl groups at both terminals according to the present invention can react with a polymer (I) having hydroxyl groups at both terminals and a hydroxyl group. A compound (II) having two or more functional groups in one molecule as an essential component, wherein the polymer (I) has the following general formula (1): HO-A- (S ) X -B-OH (1) (In the formula, A and B each represent a divalent organic group, x
Is an integer of 2 to 5. In the method in which the polymerization of the vinyl monomer (b) is carried out using the radical polymerization initiator (c) in the presence of the compound (a) represented by the formula (1), the compound (a) is reacted in the reactor. Always 5 of radical polymerization initiator (c)
It was obtained by carrying out the above-mentioned polymerization, while making it exist in an amount of 0 mol times or more, and substantially not using anything other than the compound (a), the vinyl-based monomer (b) and the radical polymerization initiator (c). It is characterized by being a thing.

In the following, first, a polymer (I) having hydroxyl groups at both ends, which is a component contained in the composition according to the present invention (hereinafter, "polymer (I) having hydroxyl groups at both ends" is referred to as "heavy-weight". The polymer (I) may be referred to as "polymer (I)" and a method for producing the polymer (I) in the presence of the compound (a) represented by the general formula (1). In the method in which the polymerization of the monomer (b) is carried out using the radical polymerization initiator (c), the compound (a) is kept in the reactor at 5 times the radical polymerization initiator (c) during the reaction.
It is a method of carrying out the above-mentioned polymerization by making it exist at 0 mol times or more and substantially not using other than the compound (a), the vinyl-based monomer (b) and the radical polymerization initiator (c).

Compound (a) represented by the general formula (1)
The specific example of is not particularly limited, for example,
Bis (hydroxymethyl) disulfide, bis (hydroxymethyl) trisulfide, bis (hydroxymethyl) tetrasulfide, bis (hydroxymethyl) pentasulfide, bis (2-hydroxyethyl) disulfide, bis (2-hydroxyethyl) trisulfide,
Bis (2-hydroxyethyl) tetrasulfide, bis (2-hydroxyethyl) pentasulfide, bis (3
-Hydroxypropyl) disulfide, bis (3-hydroxypropyl) trisulfide, bis (3-hydroxypropyl) tetrasulfide, bis (2-hydroxypropyl) disulfide, bis (2-hydroxypropyl) trisulfide, bis (2-hydroxy) Propyl)
Tetrasulfide, bis (4-hydroxybutyl) disulfide, bis (4-hydroxybutyl) trisulfide, bis (4-hydroxybutyl) tetrasulfide,
Bis (8-hydroxyoctyl) disulfide, bis (8-hydroxyoctyl) trisulfide, bis (8
-Hydroxyoctyl) tetrasulfide and other hydroxyalkyl di-, tri-, tetra- or penta-sulfides and their ethylene oxide adducts or propylene oxide adducts; 2,2'-dithiodiglycolic acid, 2,2'trithiodiglycolic acid , 2,2'-tetrathiodiglycolic acid, 3,3'-dithiodipropionic acid, 3,3'-trithiodipropionic acid, 3,3'-
Tetrathiodipropionic acid, 3,3'-pentathiodipropionic acid, 4,4'-dithiodibutanoic acid, 4,4'-
Trithiodibutanoic acid, 4,4'-tetrathiodibutanoic acid, 8,8'-dithiodioctanoic acid, 8,8'-trithiodioctanoic acid, 8,8'-tetrathiodioctanoic acid,
2,2'-dithiodibenzoic acid, 2,2'-trithiodibenzoic acid, 2,2'-tetrathiodibenzoic acid, 2,2'-
Di (2-hydroxyethyl) ester (ethylene oxide adduct) of di-, tri- or tetrasulfide-dicarboxylic acids such as dithiodinicotinic acid, 2,2'-trithiodinicotinic acid and 2,2'-tetrathiodinicotinic acid
Alternatively, di (hydroxypropyl) ester (propylene oxide adduct) and the like can be mentioned, and these can be used alone or in combination of two or more.

The vinyl-based monomer (b) is not particularly limited as long as it is a conventionally known vinyl-based monomer. For example, (meth) acrylic acid; methyl (meth) acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Acid (meth) acrylic acid alkyl esters such as stearyl; (meth) acrylic acid aryl esters such as benzyl (meth) acrylate; (meth) acrylic acid 2-
(Meth) acrylic acid substituent-containing alkyl ester such as hydroxyethyl, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, and γ- (methacryloyloxypropyl) trimethoxysilane. (Meth) acrylic acid derivatives such as methoxyethyl (meth) acrylate and ethylene oxide adducts of (meth) acrylic acid; (meth)
Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, ( (Meth) acrylic acid perfluoroalkyl esters such as 2-perfluoroethyl acrylate;
(Meth) acrylic acid-based monomers such as; styrene, vinyltoluene, α-methylstyrene, chlorostyrene, aromatic vinyl-based monomers such as styrene sulfonic acid and sodium salt thereof; (meth) acrylic acid perfluoromethyl , (Meth) acrylic acid trifluoromethylmethyl,
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; vinyltrimethoxysilane, vinyltriethoxysilane, γ- (methacryloyloxypropyl) trimethoxysilane, etc. Silicon-containing vinyl unit Maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecyl Maleimide derivatives such as maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide; vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; vinyl monomers containing amide groups such as acrylamide and methacrylamido; vinyl acetate , Vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc .; 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-based monomer (b)
May have a functional group such as a hydroxyl group, a carboxyl group or an amino group in the molecule. When a relatively high crosslink density is required, for example, in coating applications, it is rather preferable to use a small amount of a vinyl monomer having a functional group. 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 The amount of the vinyl-based monomer having 1 to 50% by weight is preferably 1 to 50% by weight, more preferably 5 to 30% by weight. In the case of a vinyl monomer having a carboxyl group, the vinyl monomer having a carboxyl group is 0.5 to 25% by weight based on the total amount of the vinyl monomer (b) used. Is preferred and 1 to 10% by weight is more preferred.

The vinyl-based monomer (b) is used as described above.
There is no particular limitation as long as it is a conventionally known vinyl monomer,
For example, when transparency, weather resistance, water resistance, and the like are required, it is preferable to use a (meth) acrylic acid-based monomer as a main component. In this case, it is preferable that the (meth) acrylic acid-based monomer be contained in an amount of 40% by weight or more based on the entire vinyl-based monomer (b).

When gloss and hardness of the coating film are required, it is preferable to use an aromatic vinyl monomer.
In this case, it is preferable that the aromatic vinyl monomer is contained in an amount of 40% by weight or more based on the entire vinyl monomer (b). 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 monomer is contained in an amount of 10% by weight or more based on the entire vinyl monomer (b).

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 monomer is contained in an amount of 10% by weight or more based on the entire vinyl monomer (b). The radical polymerization initiator (c) is not particularly limited, but examples thereof include isobutyryl peroxide, cumyl peroxyneodecanoate, diisopropyloxydicarbonate, di (n-propyl) peroxydicarbonate, di (2- Ethoxyethyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxypivalate, t-butyl Peroxypivalate, 3,3,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxyoctate, succinic acid peroxide, acetyl peroxide, t-butyl peroxy (2-ethylhexa) Nate), m Toluoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, 1,1'-bis (t-butylperoxy) cyclohexane, t-butylperoxymaleic acid, t-butylperoxylaurate, cyclohexanone Peroxide, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxyhexane, t-butylperoxyacetate, 2,2'-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4'-bis (t-butylperoxy) valerate, di- (t-butylperoxy) isophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5 -Dimethyl-2,5-di (t-butylperoxy) Sun, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, diisobutylbenzene hydroperoxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2 , 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,1,3,3, -tetramethylbutylhydroperoxide, cumene hydroperoxide, t-butylhydroperoxide and the like. Organic peroxides; inorganic peroxides such as hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate; 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-
Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1)
-Carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,
4-dimethylvaleronitrile, 2,2'-azobis (2
-Amidinopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine),
2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2'-azobis (isobutyramide) dihydrate, 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2
-Cyanopropanol) and other azo compounds; hydrogen peroxide-Fe (II) salt, persulfate-sodium bisulfite, cumene hydroperoxide-Fe (II) salt, redox initiators such as benzoyl peroxide-dimethylaniline Other examples include photosensitizers such as diacetyl, dibenzyl and acetophenone, and only one of them may be used, or a combination of two or more thereof may be used.

However, many initiators having various functional groups such as hydroxyl group, amino group and carboxyl group have high hydrophilicity, and most of them are soluble in lipophilic vinyl monomers. Many do not. In this regard, initiators having no various functional groups are often lipophilic and are easily dissolved in various vinyl monomers, so that they are easy to use and are preferable.

In the method for producing the polymer (I), the molar ratio ((a) / (c)) between the compound (a) and the radical polymerization initiator (c) in the reactor is always maintained during the reaction. It must be 50 or more, more preferably 60 or more, and most preferably 100 or more. In the method for producing the polymer (I), components other than the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c) are not substantially used in the polymerization process. .
Specifically, the components other than the compound (a), the vinyl-based monomer (b) and the radical polymerization initiator (c) account for 10 parts of the total.
Make sure to keep the weight percentage below. And (a),
Components other than (b) and (c) are preferably 5% by weight or less, and most preferably not used at all.

In the polymerization process of the method for producing the polymer (I), the molar ratio of the compound (a) to the radical polymerization initiator (c) ((a) / (c)) in the reactor during the polymerization. ) Is
Any polymerization method may be used as long as it is always 50 or more. For example, the compound (a), the vinyl-based monomer (b) and the radical polymerization initiator (c) may be charged all at once from the beginning to carry out the polymerization, or the components may be supplied to the polymerization system at any time during the polymerization. You may go. First, at least a part of the required amount of the compound (a) is charged in a polymerization vessel in advance, and the vinyl monomer (b) and the radical polymerization initiator (c) are added thereto, and if necessary, The polymerization may be carried out by a method of feeding (feeding) the compound (a) with (a). In this case, considering the operability, the radical polymerization initiator (c) is added to the vinyl monomer (b).
Since it is preferable to supply it as a solution of (1), it is preferable to use an initiator which is sufficiently dissolved in the vinyl-based monomer (b) as the initiator (c). When the initiator (c) is hardly soluble in the vinyl monomer (b), a solvent may be used in combination as long as the object of the present invention is not impaired. At this time, the vinyl monomer (b) is contained in the compound (a).
If the radical polymerization initiator (c) and the radical polymerization initiator (c) are continuously supplied, the polymerization reaction becomes milder and control becomes very easy. However, the supply of the vinyl monomer (b) and the radical polymerization initiator (c) into the compound (a) may be intermittent.

In the method for producing the polymer (I), the amount ratio of the compound (a) and the vinyl monomer (b) used is not particularly limited, but radicals generated from the initiator (c) are Vinyl monomer (b) directly without chain transfer to compound (a)
In order to further reduce the decrease in the number of terminal hydroxyl groups Fn (OH) per one molecule of the polymer due to a side reaction of addition of the compound (a) to the vinyl-based monomer (b), Is preferable. More specifically, the weight ratio of the compound (a) and the vinyl-based monomer (b) (compound (a)
/ Vinyl monomer (b)) is preferably 0.5 or more, more preferably 1.0 or more.

The polymerization vessel used in this production method may be a batch type such as a flask type or a kneader, a piston flow tube type, or a twin-screw extruder or a continuous type depending on the viscosity of the polymer. A continuous kneader or the like 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 And from the viewpoint of good productivity, a tubular reactor,
It is preferable to use 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.

The structure of the tubular reactor is not particularly limited, and is conventionally known such as a single-tube type, a multi-tube type, or a mixer having no moving parts (made by Noritake Company or Sumitomo Sulzer). Although a tubular 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, as for the extruder and the continuous kneader, a conventionally known extruder such as a single-screw extruder or a twin-screw extruder can be used. However, from the viewpoint of mixing and heat exchange efficiency, a twin-screw extruder is used. It is preferable to use a continuous kneader.

The polymerization temperature in the method for producing the polymer (I) 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 this production method, the reaction can be carried out under pressure in an autoclave or an extruder.

Polymer (I) produced in this manner
The average molecular weight is not particularly limited, but the number average molecular weight is 500 to 10,000 in order to more exert the characteristics resulting from having reactive hydroxyl groups at both ends.
It is preferably 0, and more preferably 1000 to 10000. The average number of terminal hydroxyl groups (Fn (OH)) of the polymer (I) produced in this manner is ideally 2.0, but if it is 1.8 to 2.0, it is almost the same. It is very preferable because it can exhibit the same physical properties as the ideal one. If it is at least 1.5, physical properties close to ideal ones can be exhibited. For this reason, the average number of terminal hydroxyl groups of the polymer to be obtained (Fn (OH))
Should be 1.5 or more.

The polymer (I) has hydroxyl groups at both terminals,
A polymerizable unsaturated group such as vinyl group, an amino group, a carboxyl group, an ethynyl group, an epoxy group, a silanol group, an alkoxysilyl group, a hydrosilyl group, a mercapto group, an oxazoline group can be easily produced by utilizing a conventionally known organic reaction. ,
It can be converted into useful terminal functional groups such as maleimide group, azlactone group, lactone group, bromine and chlorine.

Next, the composition according to the present invention will be described. As described above, the composition of the present invention comprises, as described above, a polymer having a hydroxyl group at both ends (polymer (I)) obtained by the above production method and two functional groups capable of reacting with the hydroxyl group in one molecule. The compound (II) having the above is included as an essential component. As the polymer (I), one type may be used alone, or two or more types may be used in combination. Further, the weight ratio of the polymer having hydroxyl groups at both ends and the compound (II) contained in this composition (polymer (I) / compound (II))
Is not particularly limited, but is 99.99 / 0.01 to 4
It is preferably 0/60, and 99.9 / 0.1-6
It is more preferably 0/40.

The composition of the present invention comprises, in addition to the polymer (I) obtained by the above-mentioned production method, a conventionally known low molecular weight compound having a hydroxyl group and a conventionally known polymer having an hydroxyl group (acrylic polyol, polyether polyol). , Polyester polyol, polycarbonate polyol, polybutadiene polyol, polyolefin polyol, etc.).

Two functional groups capable of reacting with a hydroxyl group are contained in one molecule.
The compound (II) having two or more groups is not particularly limited, but examples thereof include a compound (e) having two or more isocyanate groups in one molecule, an amino group such as a methylolated melamine and an alkyl ether compound or a low condensation product thereof. Examples thereof include a plast resin (f), a polyfunctional carboxylic acid and a halide thereof, and a compound (g) having two or more carboxyl groups in one molecule.

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 of conventionally known compounds can be used. For example, tolylene diisocyanate, 4,4
4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate,
Isocyanate compounds such as meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate; Isocyanate compounds; Desmodur IL, HL (Bayer A.
G. FIG. Polyisocyanate compounds having an isocyanurate ring such as Coronate EH (manufactured by Nippon Polyurethane Industry Co., Ltd.); adduct polyisocyanate compounds such as Sumidur L (manufactured by Sumitomo Bayer Urethane Co., Ltd.); Coronate HL (Japan) Adduct polyisocyanate compounds such as those manufactured by Polyurethane Co., Ltd.). These can be used alone or in combination of two or more. Further, a blocked isocyanate may be used.

In order to take advantage of the excellent weather resistance of the composition containing the polymer (I) and the polyfunctional isocyanate compound (e), the polyfunctional isocyanate compound (e) is used.
As, for example, hexamethylene diisocyanate,
It is preferable to use an isocyanate compound having no aromatic ring, such as hydrogenated diphenylmethane diisocyanate and Sumidur N (manufactured by Sumitomo Bayer Urethane Co., Ltd.).

The compounding ratio of the polymer (I) to the polyfunctional isocyanate compound (e) having two or more isocyanate groups in one molecule is not particularly limited,
For example, the ratio of the isocyanate group of the compound (e) to the hydroxyl group of the polymer (I) (NCO / O
H (molar ratio)) is preferably 0.5 to 1.5, and more preferably 0.8 to 1.2. However, when this composition is used for applications requiring excellent weather resistance, the composition may be used in a molar ratio of up to about NCO / OH = 3.0.

In order to accelerate the urethanization reaction between the polymer (I) which is a component in the composition of the present invention and the polyfunctional isocyanate compound (e), an organotin compound or an organic tin compound may be added, if necessary. The use of known catalysts such as tertiary amines is free. The aminoplast resin (f) used in the composition of the present invention is not particularly limited,
Examples thereof include a reaction product of a triazine ring-containing compound represented by the following general formula 1 with formaldehyde (methylol compound), a low condensation product of the triazine ring-containing compound and formaldehyde, a derivative thereof, and a urea resin. To be

[0042]

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(In the formula, X represents an amino group, a phenyl group, a cyclohexyl group, a methyl group or a vinyl group.) The triazine ring-containing compound represented by the above general formula 1 is not particularly limited, but for example, , Melamine, benzoguanamine, cyclohexanecarboguanamine, methylguanamine, vinylguanamine and the like. These may be used alone or in combination of two or more.

The reaction product of the triazine ring-containing compound and formaldehyde or a derivative thereof is not particularly limited, and 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- bond and /
Or low condensation products or an alkyl etherified formaldehyde resin was several bonded via -NH-CH ₂ -NH- bond (manufactured by Cymel (manufactured by Mitsui Cyanamid Co.)) 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 between the triazine ring-containing compound and formaldehyde used when synthesizing the compound varies depending on the intended use. It is preferably in the range of 6. Next, the polymer (I) and the aminoplast resin (f) in the composition of the present invention containing the polymer (I) and the aminoplast resin (f) as the compound (II) as essential components.
The ratio (weight ratio) is preferably 95: 5 to 50:50, and more preferably 80:20 to 60:40.

In the composition of the present invention containing the polymer (I) and the aminoplast resin (f) as essential components, conventionally known catalysts such as paratoluenesulfonic acid and benzenesulfonic acid are added to accelerate the reaction. It is free to use. 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, adipic acid, phthalic acid, phthalic anhydride, terephthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid A polyfunctional carboxylic acid such as diphenic acid or naphthalenedicarboxylic acid or an anhydride thereof, and a halide thereof,
Examples thereof include polymers having a plurality of carboxyl groups. As the compound (g), one type may be used alone, or two or more types may be used in combination. The molar ratio of the compound (g) to the hydroxyl group in the polymer (I) (compound (g) / hydroxyl group in the polymer (I)) is preferably 1 to 3, and 1 to 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 (I) used for coating, a polymer having a hydroxyl value of about 20 to 200 is preferable. That is, when a monomer having a hydroxyl group is not copolymerized, the number average molecular weight of the polymer (I) is preferably about 500 to 5,000. However, even those having a number average molecular weight of more than 5000 can be used by copolymerizing a monomer having a hydroxyl group. The Tg of the polymer (I) used for paints is -3.
0 degreeC-100 degreeC is preferable, and -10 degreeC-60 degreeC is more preferable. By adjusting the type and ratio of the vinyl monomer (b) to be used, a polymer having a desired Tg can be synthesized. When the aminoplast resin (f) is used as the compound (II), 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 (I), a conventionally known low-molecular compound having a hydroxyl group, a conventionally known polymer having a hydroxyl group (acrylic polyol, polyether 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 (I) is preferably −20 ° C. or lower, and its molecular weight (weight average molecular weight) is from 1000 to 1,000. It is preferably 1,000,000. 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, in the composition, if necessary, conventionally known resins for pressure-sensitive adhesives, tackifiers, plasticizers, fillers and antiaging agents. And the like. The tackifier that can be used is not particularly limited, and examples thereof include rosin-based, rosin ester-based, polyterpene resin, and chroman-
Examples thereof include indene resin, petroleum resin, and terpene phenol resin. The plasticizer is not particularly limited, and 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. The tackifiers, plasticizers, fillers and antioxidants listed above are
For each, only one kind may be used, or two or more kinds may be used in combination.

When the composition of the present invention is used as an adhesive composition, the molecular weight of the polymer (I) (weight average molecular weight)
Is preferably 1000 to 1,000,000.
By combining this polymer (I) with a conventionally known isocyanate compound or the like, it can be used as a one-pack or two-pack 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, but, for example, ethylene glycol (also referred to as EG) as low molecular weight polyols,
Diethylene glycol (also called DEG), dipropylene glycol (also called DPG), 1,4-butanediol (also called 1,4-BD), 1,6-hexanediol (also called 1,6-HD), neopentyl Glycol (also called NPG), trimethylolpropane (TM
P), etc., and polyether polyol [polyethylene glycol (P
EG), 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. Although it does not specifically limit as a tackifier, For example, a terpene resin, a phenol resin, a terpene-phenol resin, a rosin resin, a xylene resin, etc. can be mentioned. The coupling agent is not particularly limited, and 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. Examples of the thixotropic agent include, but are not particularly limited to, Aerosil and Disparone. 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 may be used alone or in combination of two or more. Good.

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 cosmetic paper, an adhesive for wood, a structural adhesive (automobile,
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 composition for artificial leather and / or synthetic leather, all conventionally known compounds used for artificial leather or synthetic leather should be used in this composition, if necessary. Can be done. For example, a chain extender, a high molecular weight polyol, an organic isocyanate, a solvent and the like. The chain length extender is not particularly limited, but for example, as the polyol chain length extender, EG, DEG, triethylene glycol (also referred to as TEG), DPG, 1,4-B.
D, 1,6-HD, NPG, hydrogenated bisphenol A and the like, and examples of the polyamine chain length extender include:
4,4'-diaminodiphenylmethane, tolylenediamine, 4,4'-diaminodicyclohexylmethane, piperazine and the like can be mentioned, and only one of them may be used, or two or more thereof may be used in combination. . As the high molecular weight polyol, polyether polyol (PEG, P
One or more of PG, EO / PO copolymer, PTMEG), polyester polyol, castor oil, liquid polybutadiene, polycarbonate diol, acrylic polyol and the like are used. As the organic isocyanate, 4,4′-diphenylmethane diisocyanate (M
Also called DI), toluylene diisocyanate (TDI
(Also referred to as), isophorone diisocyanate, hexamethylene diisocyanate, etc., or two or more of them are used. As the solvent, dimethylformamide (DMF
Methyl ethyl ketone (also called MEK),
One or two of toluene, xylene, tetrahydrofuran (also called THF), dioxane, cellosolve acetate, isopropyl alcohol (also called IPA), ethyl acetate, butyl acetate, cyclohexanone, methyl isobutyl ketone (also called MIBK), acetone, etc. More than one seed is used. If necessary, an isocyanate compound having three or more functionalities can be used as a crosslinking agent. In addition, if necessary, urethanization catalysts, accelerators, pigments, dyes, surfactants, textile softeners, ultraviolet absorbers, antioxidants, hydrolysis inhibitors, fungicides, inorganic fillers, organic fillers , Matting agents, defoaming agents and the like can also be used. The composition can be used for artificial leather, synthetic leather of a dry method and synthetic leather of a wet method.

When the composition of the present invention is used as a printing ink composition, any conventionally known compounds used for printing inks can be used in this composition, if necessary. For example, a chain extender, a high molecular weight polyol, an organic isocyanate, a solvent and the like. The chain length extender is not particularly limited, but examples of the polyol chain length extender include EG, DEG, TEG, DPG,
1,4-BD, 1,6-HD, aliphatic glycol such as neopentyl glycol, alicyclic glycol such as 1,4-cyclohexane glycol, xylylene glycol, 1,4-dihydroxyethylbenzene, hydrogenated bisphenol Aromatic glycols such as A are listed,
As the polyamine chain extender, aliphatic diamines such as ethylenediamine and propylenediamine, alkanolamines such as monoethanolamine and diethanolamine, 4,4′-diaminodiphenylmethane, tolylenediamine and 4,4′-diaminodicyclohexyl. Examples thereof include methane and piperazine, and these may be used alone or in combination of two or more. As the high molecular weight polyol, polyether polyol (P
One or more of EG, PPG, EO / PO copolymer, PTMEG), polyester polyol, liquid polybutadiene, polycarbonate diol, etc. may be mentioned. Examples of the organic isocyanate include 1,5-naphthylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, toluylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. May be used alone or in combination of two or more. Examples of the solvent include alcohols such as ethanol and isopropanol, ketones such as acetone, MEK, MIBK, and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, trichlene, and perkle, THF, and the like. The ethers such as dioxane, the esters such as cellosolve acetate, ethyl acetate and butyl acetate may be used alone or in combination of two or more. If necessary, an isocyanate compound having three or more functionalities can be used as a crosslinking agent. In addition, if necessary, a urethanization catalyst, an accelerator, a colorant such as a pigment, a surfactant, an ultraviolet absorber, an antioxidant, a hydrolysis inhibitor and the like can be used. In addition, in the production of the printing ink composition, it is possible to mix polymers such as nitrocellulose, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyamide, and acrylic acid ester-based polymer, if necessary.

When the composition of the present invention is used as a thermosetting polyurethane elastomer composition, the composition may optionally contain all the conventionally known compounds used in ordinary thermosetting polyurethane elastomer compositions. Can be used. For example, chain length extenders, curing agents, high molecular weight polyols, organic isocyanates, etc. The chain length extender is not particularly limited, but, for example, as the polyol chain length extender, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4- Aliphatic glycols such as butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, alicyclic glycols such as 1,4-cyclohexaneglycol, Xylylene glycol,
Aromatic glycols such as 1,4-dihydroxyethylbenzene and hydrogenated bisphenol A may be used, and these may be used alone or in combination of two or more. As the curing agent, 3,3'-dichloro-4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, o- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, 4,
4'-diamino-3,3'-dimethyldiphenyl, 1,
5-naphthylenediamine, tris (4-aminophenyl) methane, trimethylene glycol-di-p-aminobenzoate, 2,6-dichloro-p-phenylenediamine, 4,4'-diamino-3,3'-dimethoxy Carbonyldiphenylmethane, 2,2′-diaminodiphenyldithioethane, 1,2-bis (2-aminophenylthio) ethane, trimethylene glycol-di-p-aminobenzoate, di (methylthio) tolylenediamine and the like, These may be used alone or in combination with 2
More than one species may be used in combination. Polyether polyols (PEG, PPG, EO /
PO copolymer, PTMEG), polyester polyol, liquid polybutadiene, polycarbonate diol,
One or more of castor oil and the like are used. Examples of the organic isocyanate include 1,5-naphthylene diisocyanate, 1,4-phenylene diisocyanate, carbodiimide-modified diphenylmethane diisocyanate,
4,4-diisocyanate-3,3-dimethyldiphenyl, 4,4′-diphenylmethane diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, toluylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate,
One or more of 1,3- or 1,4-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, bis (isocyanatomethyl) cycloxane and the like are used. If necessary, a solvent may be used. For example, alcohols such as ethanol and isopropanol, ketones such as acetone, MEK, MIBK and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, tricrene, perchrene, THF, dioxane, etc. And one or more of esters such as ethers, cellosolve acetate, ethyl acetate and butyl acetate. In addition, if necessary, urethanization catalysts, accelerators, coloring agents such as pigments, surfactants, ultraviolet absorbers, antioxidants, hydrolysis inhibitors, fillers, defoamers, and the like can be used.

In the urethanization step, conventionally known one-shot method, prepolymer method and the like can be used. The use of the thermosetting polyurethane elastomer composition is not particularly limited, but includes, for example, rolls, solid tires, casters, various gears, connection rings and the like.
Examples include a liner and a belt.

When the composition of the present invention is used as a resin composition for flooring, any conventionally known compound used in the resin composition for flooring may be used in this composition, if necessary. I can. For example, curing agents, high molecular weight polyols, organic isocyanates, and the like. As a curing agent,
Although not particularly limited, examples of the polyol-based curing agent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, glycerin, aliphatic glycols such as trimethylolpropane, alicyclic glycols such as 1,4-cyclohexaneglycol, xylylene glycol, 1,4- Aromatic glycols such as dihydrooxyethylbenzene and hydrogenated bisphenol A are listed, and examples of the amine-based curing agent include 3,3′-dichloro-4,4′diaminodiphenylmethane, 4,4-diaminodiphenylmethane, o- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine,
4,4'-diamino-3,3'-dimethyldiphenyl,
1,5-naphthylenediamine, tris (4-aminophenyl) methane, trimethylene glycol-di-p-aminobenzoate, 2,6-dichloro-p-phenylenediamine, 4,4′-diamino-3,3 ′ -Dimethoxycarbonyldiphenylmethane, 2,2'-diaminodiphenyldithioethane, methylenedianiline NaCl complex,
4,4'-methylenebis-o-chloroaniline, 1,2
-Bis (2-aminophenylthio) ethane, trimethylene glycol di-p-aminobenzoate, di (methylthio) tolylenediamine, ethylenediamine, triethylenetetramine, hexamethylenediamine carbamate, etc., and these are one kind. They may be used alone or in combination of two or more. As the high molecular weight polyol, polyether polyol (PEG, PPG, E
One or more of O / PO copolymer, PTMEG), polyester polyol, polymer polyol, liquid polybutadiene, polyolefin polyol, polycarbonate diol, castor oil and the like are used. As the organic isocyanate, 1,5-naphthylene diisocyanate, 1,4-phenylene diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, 4,
4'-diisocyanate-3,3'-dimethyldiphenyl, 4,4'-diphenylmethane diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, toluylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate,
One or more of 1,3- or 1,4-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, bis (isocyanatomethyl) cycloxane and triphenylmethane triisocyanate are used. If necessary, a solvent may be used. For example, alcohols such as ethanol and isopropanol, ketones such as acetone, MEK, MIBK and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, tricrene, perchrene, THF, dioxane, etc. And one or more of esters such as ethers, cellosolve acetate, ethyl acetate and butyl acetate. In addition, if necessary, a urethanization catalyst, an accelerator, a plasticizer, a tackifier, a coloring agent such as a pigment, a surfactant, an ultraviolet absorber, an antioxidant, a hydrolysis inhibitor, a filler, and a defoaming agent. Agents and the like can be used.

The use of the resin composition for flooring materials is not particularly limited, but examples thereof include flooring materials for ships and buildings, coating film waterproofing agents, sheet waterproofing agents, spray waterproofing agents, sealing materials, artificial grass, etc. Adhesives, asphalt modifiers for road pavements, elastic pavement materials for tennis courts and athletic fields, and concrete protection materials for painted floor materials. When the composition of the present invention is used as a urethane foam composition, the polymer (I) has a molecular weight (weight average molecular weight) of 1000 to 10
It is preferably 00000.

When the composition of the present invention is used as a urethane foam composition, in the composition, if necessary, conventionally known polyols (other than the polymer (I) obtained by the above-mentioned production method, Low molecular weight polyols, high molecular weight polyols, etc.), polyisocyanate (eg TDI, MDI etc.), catalyst (eg amine type, tin type etc.), water, surfactant (eg silicon type, non-ionic type, (Ionic type, etc.), additives (for example, flame retardant, antimicrobial agent, coloring agent, filler, stabilizer, etc.), foaming aid (for example, halogenated hydrocarbon, etc.) and the like may be contained.

When the composition of the present invention is used as a sealant composition, the polymer (I) preferably has a molecular weight (weight average molecular weight) of 1,000 to 1,000,000. When the composition of the present invention is used as a sealant composition, the composition may contain, if necessary, conventionally known polyols (high molecular weight polyols other than the polymer (I) obtained by the above production method). Etc.), polyisocyanates (eg 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 (also called DOP), phthalic acid) Di-i-decyl (also called DIDP), dioctyl adipate (DOA
Etc.), anti-sagging agents (eg, colloidal silica, hydrogenated castor oil, organic bentonite, surface-treated calcium carbonate, etc.), anti-aging agents (eg, hindered phenols, benzotriazole, hindered amines, etc.) And a foaming inhibitor (eg, a dehydrating agent, a carbon dioxide gas absorbent, etc.).

When a polymer obtained by converting the hydroxyl group of the polymer (I) obtained by the above-mentioned production method into a hydroxysilyl group, an alkoxysilyl group or a mercapto group is used as an essential component of a sealant composition, its sealing is achieved. The material composition becomes a sealing material composition having a crosslinking system different from urethane. Next, a polymer having a polymerizable unsaturated group at both ends will be described.

The polymer having a polymerizable unsaturated group at both ends is obtained by reacting the polymer (I) obtained by the above-mentioned production method with two types of reaction of a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group. It can be obtained by further reacting the compound (h) having a functional group in one molecule. When synthesizing the polymer having a polymerizable unsaturated group at both ends, two kinds of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group, which are reacted with the polymer (I), are used. The compound (h) that is also contained in the molecule 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 dimethyl benzyl isocyanate, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and carboxyl groups of these. Examples thereof include halides and vinylguanamine methylol compounds.

In this reaction, it is free to use a solvent or a conventionally known catalyst. Examples of this catalyst include:
When the functional group of the compound (h) is an isocyanate group, tertiary amines such as triethylamine, tin compounds such as dibutyltin dilaurate, and the like, 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 and the like, when the functional group is a methylolated triazine ring, sulfonic acids such as dodecylbenzene sulfonic acid and other weak acids are respectively included. No.

When the polymer having a polymerizable unsaturated group at both ends is used as an essential component of the resin composition, other components contained in the resin composition include, for example, 1
Examples thereof include vinyl monomers having one polymerizable unsaturated group in the molecule. The vinyl monomer is not particularly limited, and a conventionally known vinyl monomer can be used without any problem. For example, those described above as examples of the vinyl monomer (b) can be mentioned. If necessary, a conventionally known polymerization initiator may be contained in the resin composition. The energy source for initiating the polymerization is not particularly limited, but for example, light, EB, UV,
Radiation, heat, etc. can be used.

Examples of the resin composition containing as an essential component a polymer having a polymerizable unsaturated group at both terminals and a vinyl monomer having one polymerizable unsaturated group in one molecule are:
Examples thereof include a gel coat resin composition and a resin composition for artificial marble described in detail below. The gel coat resin composition may also contain a polyfunctional vinyl monomer (i) having two or more polymerizable unsaturated groups in one molecule, if necessary. The polyfunctional vinyl monomer (i) 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, methylenebisacrylamide, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) Acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned. These are 1
Species or a combination of two or more can be used.

The weight ratio of the polymer having a polymerizable unsaturated group at both ends contained in the gel coat resin composition to the vinyl monomer (polymer having a polymerizable unsaturated group at both ends / vinyl). The system monomer) is not particularly limited, but is 10 /
90-60 / 40 is preferable, 20 / 80-50 / 50
Is more preferred. If the ratio is smaller than 10/90, the reaction shrinkage of the gel coat resin layer is too large, so that the shrinkage strain increases and it becomes difficult to obtain a good coat surface. On the other hand, if the ratio is greater than 60/40, the viscosity of the gel coat resin composition becomes too high, and the workability tends to be extremely reduced.

To obtain the surface hardness of the gel coat layer,
The Tg of the polymer having a polymerizable unsaturated group at both ends and the Tg of the vinyl monomer used for this purpose are both 2
The temperature is preferably 0 ° C. or higher. 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 or polyfunctional in a polymer having a polymerizable unsaturated group at both ends. A polymer having a vinyl-based monomer (i) and a polymerizable unsaturated group at both ends, 1
50 based on the total amount of the vinyl-based monomer having one polymerizable unsaturated group in the molecule and the polyfunctional vinyl-based monomer (i)
It is preferably used in a proportion of not more than wt%.

If necessary, a polymerization inhibitor such as hydroquinone, catechol, 2,6-ditertiarybutylparacresol is added to the gel coat resin composition, and as described above with reference to the initiator (c). It is cured with an initiator, especially an organic peroxide initiator. In this case, a curing accelerator such as various reducing metal salts such as cobalt naphthenate, nickel naphthenate and iron naphthenate, and a reducing compound such as amines and mercaptans may be used in combination.

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 resin composition for artificial marble may include a polyfunctional vinyl monomer (i) having two or more polymerizable unsaturated groups in one molecule, a filler, a curing agent, a thermoplastic resin, if necessary. Additives such as polymers can be freely added.

The polyfunctional vinyl-based monomer (i) optionally added to the artificial marble resin composition is not particularly limited, but ethylene glycol di (meth) acrylate, propylene glycol di (meth) is used. Polyfunctional (meth) s such as acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate Examples thereof include acrylates, methylenebis (meth) acrylamide, divinylbenzene and the like. The addition amount of the polyfunctional vinyl-based monomer (i) is not particularly limited, but it is a polymer having a polymerizable unsaturated group at both ends, and a vinyl-based monomer having one polymerizable unsaturated group in one molecule. It is preferably 40% by weight or less based on the total amount of the polymer and the polyfunctional vinyl-based monomer (i). If the amount of the polyfunctional vinyl monomer (i) exceeds 40% by weight, the resulting artificial marble is hard and brittle, which is not desirable.

Fillers added as necessary to the resin composition for artificial marble 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 synthetic resins such as unsaturated polyester resins, thermosetting acrylic resins and melamine resins. The amount of the filler added is not particularly limited, but it is a polymer having a polymerizable unsaturated group at both ends, a vinyl monomer having one polymerizable unsaturated group in one molecule, and a polyfunctional vinyl monomer. 100 to 800% by weight is preferred with respect to the total amount of body (i). If the addition amount is less than 100% by weight, heat resistance and flame retardancy may be insufficient, and 800% by weight
If it exceeds, a polymer having a polymerizable unsaturated group at both ends,
The dispersibility of the filler in the vinyl-based monomer having one polymerizable unsaturated group in one molecule and the polyfunctional vinyl-based monomer (i) becomes insufficient, and the fluidity at the time of molding and curing becomes insufficient. It may be damaged and uniform artificial marble may not be obtained.

The hardener which is optionally added to the artificial marble resin composition is not particularly limited, and 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, preferred for press molding are t-butyl peroxyoctoate and benzoyl peroxide, which are medium- and high-temperature curing agents that give cured products having good transparency without cracking. The medium / low temperature curing agent is 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 according to need 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 polymers for reducing shrinkage such as polyethylene, polycaprolactam and saturated polyester are used alone or in combination. However, if a large amount of thermoplastic polymer for low shrinkage is blended, viscosity rises during kneading, making it difficult to obtain a casting compound with a high filler content, or in terms of product transparency and heat resistance. Sometimes you get only inferior things. Therefore, the thermoplastic polymer for low shrinkage should be used in a small amount as much as possible, and is not particularly limited, but a polymer having a polymerizable unsaturated group at both ends may be used.
1 based on the total amount of the vinyl monomer having one polymerizable unsaturated group in the molecule and the polyfunctional vinyl monomer (i).
It is preferably used in the range of not more than 00% by weight.

Next, the polymer having carboxyl groups at both ends will be described. The polymer having a carboxyl group at both ends is the polymer (I) obtained by the above production method,
It can be obtained by further reacting the compound (j) and / or an acid anhydride having two reactive groups, a functional group capable of reacting with a hydroxyl group and a carboxyl group, in one molecule.

When a polymer having a carboxyl group at both ends is synthesized, two reactive groups, a functional group capable of reacting with a hydroxyl group and a carboxyl group, which react with the polymer (I), are combined in one molecule. The compound (j) contained in the compound is not particularly limited, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and phthalic acid. , Dibasic acids such as terephthalic acid, maleic acid, fumaric acid and itaconic acid, and halogen-substituted carboxylic acids such as chloroacetic acid and bromoacetic acid. As described above, the two reactive groups of the functional group capable of reacting with the hydroxyl group and the carboxyl group of the compound (j) may be two carboxyl groups or a group other than the carboxyl group such as a halogen group. It may be a combination of a functional group and a carboxyl group. An acid anhydride may be used instead of the compound (j), or the compound (j) and the acid anhydride may be used in combination. The acid anhydride is also not particularly limited, and examples thereof include succinic anhydride, glutaric anhydride, phthalic anhydride, maleic anhydride, and itaconic anhydride.

In the reaction of the polymer (I) with the compound (j) and / or the acid anhydride, it is free to use a solvent or a conventionally known catalyst. Examples of the catalyst include an inorganic acid such as sulfuric acid and hydrochloric acid, an inorganic base such as sodium hydroxide and potassium hydroxide when the functional group capable of reacting with a hydroxyl group of the compound (j) is a carboxyl group, When a tertiary amine compound such as triethylamine or pyridine, or an organic acid salt such as sodium acetate or potassium acetate is a halogen group, a tertiary amine compound such as pyridine or triethylamine is used.
Secondary amine compounds.

The reaction temperature when the functional group capable of reacting with the hydroxyl group of the compound (j) is a carboxyl group (for example, when the compound (j) is a dibasic acid) is not particularly limited, but 60 -100 degreeC is preferable. If the temperature is lower than 60 ° C., the reaction rate is low and the final conversion is low.
On the other hand, when the temperature exceeds 100 ° C., the reaction rate of the dibasic acid increases, but problems such as an increase in the amount of diester formed and an increase in the molecular weight after the reaction occur.

Next, a resin containing as an essential component a polymer having a carboxyl group at both ends and a compound (k) having two or more functional groups capable of reacting with the carboxyl group in one molecule. The composition will be described. The polymers having carboxyl groups at both ends may be used alone or in combination of two or more. The weight ratio of the polymer having a carboxyl group at both ends to the compound (k) (polymer having a carboxyl group at both ends / compound (k)) contained in this resin composition is not particularly limited. Is preferably 99.99 / 0.01 to 40/60, and more preferably 99.9 / 0.1 to 60/40.

The compound (k) 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,
Compounds having two or more aziridine groups in one molecule, 1
Examples include a compound having two or more ester groups in a molecule, a compound having two or more carboxyl groups in a molecule, and the like.

The polymer having a carboxyl group at both ends 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, Brominated bisphenol A
Examples thereof include glycidyl ethers of phenols; 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.

If desired, additives such as fillers, pigments and curing agents may be added to the above epoxy resin composition. 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, natural crushed stones such as marble, limestone, pyroxene, amphibole, sandstone, granite, basalt, unsaturated polyester resin, thermosetting acrylic resin and melamine resin, etc. And crushed synthetic resin. 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 anhydride, dodecylsuccinic anhydride, pyroanhydride Acid anhydrides such as melitic acid, methylcyclohexenetetracarboxylic anhydride, trimellitic anhydride, polyazeleic anhydride; phenolic hydroxyl-containing compounds such as phenol novolak and cresol novolac; polymercaptans;
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. And one or more of these latent curing agents can be used.

Next, it is obtained by reacting the polyol component (l) containing the polymer (I) as an essential component with the polyfunctional isocyanate compound (e) having two or more isocyanate groups in one molecule. , Polyurethane will be described. The polyfunctional isocyanate compound (e) having two or more isocyanate groups in one molecule used in synthesizing the polyurethane is as described above. The polyol component (l) containing the polymer (I) as an essential component is not particularly limited as long as it is a polyol other than the polymer (I), but if necessary, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol. , 1,4-butanediol,
1,3-butanediol, 1,6-hexanediol,
Low molecular weight polyols such as trimethylolpropane and pentaerythritol, and polyether polyols such as polyethylene glycol, polypropylene glycol, polypropylene glycol-polyethylene glycol block copolymers, low molecular weight polyols mentioned above and phthalic acid, phthalic anhydride, terephthalic acid, maleic Polyene polyol synthesized from polyfunctional carboxylic acid such as acid, maleic anhydride, fumaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, polycarbonate polyol, butadiene and diene-based polyol consisting of butadiene / acrylonitrile copolymer main chain Or a combination of two or more polyols selected from polymer polyols such as polyolefin polyols, polymer polyols and acrylic polyols. It can be used Te.

In this synthesis, the total amount of the polyol component (l) and the polyfunctional isocyanate compound (e) may be reacted in one step, or the polyol component (l) may be reacted in the first step. ) And the polyfunctional isocyanate compound (e) are reacted with each other to first synthesize a polymer (oligomer) having isocyanate groups at both ends, and then the polymer (oligomer) is treated in the next step. You may use the multistep reaction which synthesize | combines polyurethane by making it react with another (or the same) polyol component, and repeating this. However, in the case of a multi-stage reaction, it may be necessary to remove the isocyanate compound remaining after the reaction on the way out of the system.

When various kinds of polyols are used as the polyol component (l) and it is desired to synthesize a polyurethane having a block structure in which sequences such as ABA, (AB) _n and ABCBA are controlled, it is preferable to use the above-mentioned multi-step reaction. . As described above, the polymer (I) is very useful as a raw material for producing various block polymers.

In this case, when the polymer (I) is used and only the compound having only two isocyanate groups in one molecule is used as the polyfunctional isocyanate compound (e), almost only the thermoplastic polymer is used. As the polymer (I), a polymer having a hydroxyl group in addition to both terminals is used, or a compound having three or more isocyanate groups in one molecule is used as the polyfunctional isocyanate compound (e). In some cases, depending on the reaction conditions, both branched thermoplastic polyurethane and thermosetting polyurethane may be obtained.

The ratio of the amount of the polymer (I) to the amount of the polyfunctional isocyanate compound (e) used in synthesizing the polyurethane is not particularly limited. For example,
In the case of the above-mentioned multi-step reaction, the molar ratio of the isocyanate group in the compound (e) and the hydroxyl group in the polymer (I) (N
CO / OH) is not a problem as long as it is higher than 1, but in order to prevent the molecular weight from increasing at this stage and synthesize polyurethane having a definite block structure, 1.2 to 2.0 is preferable and 1. 5 to 2.0 is more preferable. Moreover, the molar ratio (NCO / OH) of the isocyanate group in the polyfunctional isocyanate compound (e) and the hydroxyl group in the polymer (I) in the case of the one-step reaction is 0.5 to 1.5. Preferably, it is more preferably 0.8 to 1.2.

In synthesizing the polyurethane, any known catalyst such as an organotin compound or a tertiary amine, or various solvents may be used to promote the urethane reaction. Next, the polyester obtained by reacting the polyol component (l) containing the polymer (I) as an essential component with the compound (g) having two or more carboxyl groups in one molecule will be described.

The polyol component (l) containing the polymer (I) as an essential component, which is used when synthesizing this polyester, is the same as that described for the polyurethane. The compound (g) having two or more carboxyl groups in one molecule is also the same as described above. In addition, at the time of this synthesis, the polyol component (l),
And the total amount of the compound (g) having two or more carboxyl groups in one molecule may be reacted in one step. By reacting with a compound (g) having two or more carboxyl groups in the molecule to synthesize a polymer (oligomer) having carboxyl groups at both ends,
In the next step, the polymer (oligomer) may be further reacted with another (or the same) polyol component, and a multi-step reaction for synthesizing a polyester may be used by repeating this. However, in the case of a multi-stage reaction, it may be necessary to remove the carboxyl group-containing compound remaining after the reaction halfway out of the system.

When various kinds of polyols are used as the polyol component (l) and a polyester having a sequence-controlled block structure such as ABA, (AB) _n or ABCBA is desired to be synthesized, it is preferable to use the above-mentioned multi-step reaction. As described above, the polymer (I) is very useful as a raw material for producing various block polymers.

When synthesizing this polyester,
It is free to use a known catalyst such as an inorganic acid such as sulfuric acid or various solvents to promote the esterification reaction. When the above polyurethane and polyester are used as the thermoplastic elastomer, it is necessary that these polyurethane and polyester are thermoplastic. Therefore, when synthesizing these polyurethanes and polyesters, the main components of the polyfunctional isocyanate compound (e) and the compound (g) having two or more carboxyl groups in one molecule are two-functional isocyanate compound and bifunctional isocyanate compound. It is preferable to use a carboxylic acid,
It is also preferable to use a bifunctional polyol as the main component of the polyol component (l).

Further, in order to fully exhibit the performance as a thermoplastic elastomer, it is necessary to have a block structure in which hard segments and soft segments are regularly arranged. Therefore, it is preferable to synthesize by the above-mentioned multistep reaction. . The following additives may be added to this thermoplastic elastomer as long as practicality is not impaired. That is, glass fiber,
Inorganic fillers such as carbon fiber, boron fiber, alumina fiber, calcium carbonate, titanium oxide, mica, and talc; flame retardants such as phosphate esters; ultraviolet absorbers such as benzophenones; and hindered phenol-based oxidations such as butylhydroxytoluene And a crystallization accelerator such as highly crystallized polyethylene terephthalate.

When the above-mentioned polyurethane or polyester is used as a molding material, the molding material may further contain other components, such as glass fiber and pulp, which are contained in conventional molding materials, as other components. Release agents, pigments such as calcium carbonate and titanium oxide, ultraviolet absorbers, antioxidants and the like may be included. 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, the block polymer containing the polymer (I) obtained by the above production method as an essential component will be described. As a method of obtaining this block polymer,
Although not particularly limited, for example, the following four methods and the like can be mentioned. Two or more kinds of polyols are used as the polyol component (l) containing the polymer (I) obtained by the above production method as an essential component, and two or more functional groups capable of reacting with these hydroxyl groups are contained in one molecule. A method of reacting with a compound.

The polymer (I) obtained by the above production method, the polymer having only one hydroxyl group in one molecule, and the compound having two or more functional groups capable of reacting with the hydroxyl group in one molecule. How to react. A method of reacting the polymer (I) obtained by the above production method with a polymer having one or more functional groups capable of reacting with a hydroxyl group in one molecule.

By using the polymer (I) obtained by the above production method as an initiator and subjecting one or more cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran to ring-opening polymerization,
A method for obtaining an ABA type block polymer. In the above method, and, as the functional group capable of reacting with a hydroxyl group, is not particularly limited, for example, an isocyanate group, a carboxyl group, a triazine ring, a methylolated triazine ring, an acid anhydride, an azlactone ring, a silanol group, a 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 is used. be able to. The use of the block polymer is not particularly limited, for example, a surfactant, a compatibilizer, a resin for a toner, a hot melt adhesive, a thermoplastic elastomer, a thermosetting elastomer, a resin modifier, a pressure-sensitive adhesive, Dispersants, heat-resistant transparent resins, impact-resistant transparent resins, artificial leather, synthetic leather, cement water reducing agents, and the like.

The structure of this block polymer is not particularly limited, but it is naturally determined according to each application. For example, taking the surfactant application as an example,
The two or more types of segments constituting the block polymer are desirably composed of a hydrophilic segment and a hydrophobic segment. In the case of using a thermoplastic elastomer as an example, it is desirable that two or more types of segments constituting the block polymer have glass transition temperatures different from each other by 10 ° C. or more.

[0095]

In the method for producing the polymer (I), the molar ratio ((a) / (c)) of the compound (a) and the radical polymerization initiator (c) in the polymerization vessel during the polymerization is always 50 or more. By maintaining it at 1, the by-product of the polymer having no hydroxyl group at one end or both ends is suppressed. That is, the compound (a) and the radical polymerization initiator (c) in the polymerization vessel during the polymerization
When the molar ratio of the radical polymerization initiator is less than 50, radicals generated from the radical polymerization initiator (c) cannot be sufficiently chain-transferred to the compound (a) to start the polymerization, and no hydroxyl group is contained at one end or both ends. Polymer by-products cannot be ignored. If the molar ratio is 50 or more, such a by-product of the polymer is reduced to a practically acceptable level. Further, when the molar ratio is 60 or more, it is more preferable because the by-product of the polymer as described above is reduced to an almost negligible amount. Most preferred is that the by-product of coalescence is reduced to a negligible amount.

In the method for producing the polymer (I), components other than the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c) are not substantially used in the polymerization process. ing. Specifically, components other than the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c) are set to be about 10% by weight or less of the whole. One of the reasons why good results were obtained by doing so is as follows. That is, if a component (for example, a solvent) other than the compound (a), the polysynthetic monomer (b) and the radical polymerization initiator (c) is present in an amount of more than 10% by weight in the polymerization process, this component is used. It is considered that a side reaction such as chain transfer to the polymer increases, and a polymer having no hydroxyl group at one end or both ends is by-produced, and as a result, the value of the number of terminal hydroxyl groups decreases. However, the reason why good results can be obtained by adjusting the components other than the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c) to about 10% by weight or less of the whole is as follows. It cannot be considered only from the chain transfer constants of the vinyl monomer and the produced polymer, and many details remain unknown.

In the polymerization process of the method for producing the polymer (I), particularly in the batch type polymerization, at least a part of the required amount of the compound (a) is charged in a polymerization vessel in advance.
It is preferable to supply the vinyl-based monomer (b) and the radical polymerization initiator (c) thereto. One of the reasons why good results were obtained by doing so is as follows. That is, the compound (a)
If the polymerization is carried out after initially charging at least a part of the necessary amount of the compound (a), the compound (a) is always present in a large excess compared to the radical polymerization initiator (c) during the polymerization. The radical generated from the radical polymerization initiator (c) does not directly add to the vinyl-based monomer, but undergoes rapid chain transfer to the compound (a) to easily introduce a hydroxyl group at the polymer terminal. It is considered to be.

The polymer (I) thus obtained is
By arbitrarily selecting the type of the vinyl-based monomer (b) that constitutes the main chain, it has transparency, weather resistance, water resistance, hydrolysis resistance, and chemical resistance. The properties of polyester resin, polyurethane resin, polycarbonate resin and other various resins derived from the composition containing (I), various block polymers, and the like, which are extremely stretchable (having good bending workability) and strong. Because it demonstrates, paint, elastic wall material, floor material, waterproof film, adhesive, tackifier, adhesive, binder, sealing material, urethane foam (hard, semi-hard, soft), urethane RIM, UV・ EB cured resin, high solid paint, thermosetting elastomer, thermoplastic elastomer, various molding materials, microcellular, artificial leather, synthetic leather, elastic fiber, fiber processing agent, plasticizer Sound absorbing material, damping material, surfactant, gel coating agent, resin for artificial marble, impact resistance imparting agent for artificial marble, resin for laminated glass, raw material for reactive diluent, and various resin additives and the like. It is very useful as a raw material.

The above-mentioned polymer (I) is prepared by reacting the hydroxyl groups at both ends by a suitable method to obtain another functional group (for example, a polymerizable unsaturated group such as vinyl group, amino group, carboxyl group or acetylene group). , Epoxy group, silanol group, alkoxysilyl group, hydrosilyl group, mercapto group, oxazoline group, maleimide group, azlactone group,
(Lactone group, bromine, chlorine, etc.) can be easily converted to a polymer having both ends. These polymers are also very useful. For example, a polymer having carboxyl groups at both ends is very effective as an impact resistance imparting agent for an epoxy adhesive. In addition, by adding a plurality of ethylene oxides or propylene oxides to the terminal hydroxyl groups, it becomes a raw material such as a surfactant.

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

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

Obtained by reacting the polymer (I) with a compound (h) having in one molecule two kinds of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group. In addition to a polymer having a polymerizable unsaturated group at both ends, when a composition containing a polymerizable monomer having a polymerizable unsaturated group as an essential component is used for a gel coat resin composition application, during gel coat layer molding The reaction contraction is small, the viscosity of the gel coat resin composition during operation is low, the workability of the gel coat is good, and the hardness is high, and a tough gel coat layer having good weather resistance can be obtained.

Polyurethane obtained by reacting the polymer (I) with a polyfunctional isocyanate compound (e), and a polymer having a hydroxyl group at both ends and two or more carboxyl groups in one molecule. When the polyester obtained by reacting with the compound (g) is used as an essential component of the thermoplastic elastomer, a thermoplastic elastomer excellent in elongation, oil resistance, water resistance, weather resistance, chemical resistance and low temperature characteristics is obtained. Obtainable.

Polyurethane obtained by reacting the polymer (I) with the polyfunctional isocyanate compound (e), and the above-mentioned polymer having hydroxyl groups at both ends and 2 in 1 molecule.
When a polyester obtained by reacting with a compound (g) having at least one carboxyl group is used as an essential component of a molding material, it has excellent processability, hydrolysis resistance, weather resistance, chemical resistance and low temperature characteristics. An excellent molding material can be obtained.

[0105]

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. In the following Examples and Comparative Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. In the following, first, the polymer (I) contained in the composition of the present invention was produced according to Production Examples 1 to 24 and 58.

-Production Example 1- In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser, 153 parts of 2-hydroxyethyl disulfide (compound (a)) was charged, and nitrogen gas was slowly added. It heated at 100 degreeC, blowing. There, 1.64 parts of 2,2'-azobisisobutyronitrile (hereinafter abbreviated as "AIBN") (radical polymerization initiator (c)) was added to butyl acrylate (vinyl monomer ( b)) The solution dissolved in 64 parts was added dropwise over 30 minutes. During the dropwise addition, the polymerization temperature was maintained at 105 ± 5 ° C. The molar ratio (= (a) / (c)) between the compound (a) and the initiator (c) in the flask at the end of the dropping was 100.

After completion of the dropping, the polymerization was completed by continuing stirring at the same temperature for 30 minutes to obtain a dispersion liquid of the polymer [1].
The polymerization rate calculated from the solid content concentration of this dispersion was 96%. Subsequently, the dispersion was transferred to a separating funnel, 100 parts of toluene was added, and the mixture was shaken well, and then allowed to stand for a while to remove a lower layer (2-hydroxyethyl disulfide) separated from two phases. Thereafter, the toluene layer was washed three times with 200 parts of ion-exchanged water. Then, 50 parts of sodium sulfate were added to the washed toluene phase, and the toluene phase was dehydrated. Then, toluene and remaining monomers in the toluene phase were distilled off using an evaporator to purify the polymer [1].

The number average molecular weight of the polymer [1] after purification (M
n) was 3,600 as a result of being measured by a vapor pressure molecular weight measurement device (VPO). The average number of terminal hydroxyl groups (Fn (OH)) of the polymer [1] was determined according to JIS-K-1.
It was 2.0 (mol / mol of polymer) as a result of calculation based on the OH value 31 obtained according to 557 and the value of the number average molecular weight described above.

-Production Examples 2 to 10-In Production Example 1, the types and amounts of the compound (a), vinyl monomer (b) and radical polymerization initiator (c) used are shown in Tables 1 to 3 below. Then, the whole amount of the compound (a) was initially charged into the flask, and the radical polymerization initiator (c) dissolved in the vinyl monomer (b) was added dropwise to the flask over 1 hour, and the dropping was completed. Thereafter, Polymers [2] to [10] were obtained in the same manner as in Production Example 1 except that the polymerization was completed by continuing stirring at the same temperature for 1 hour.

The number average molecular weight of the obtained polymers [2] to [10] was determined by gel permeation chromatography (G
PC) and the average number of terminal hydroxyl groups (Fn (OH)) was determined by JI
It was calculated based on the OH value obtained according to SK-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 Production Example 1.

-Production Example 11-In Production Example 5, the compound (a) was placed in a flask at the initial stage of polymerization.
The amount of 2,2'-dithioglycolic acid di (2-hydroxyethyl) ester charged as 30 parts was
Polymer [11] was obtained in the same manner as in Production Example 5 except that the remaining 240 parts was added dropwise over 2 hours together with the vinyl-based monomer (b) in which the initiator (c) was dissolved. It was

The number average molecular weight of the obtained polymer [11] was measured by a vapor pressure molecular weight measuring device (VPO), and the average number of terminal hydroxyl groups (Fn (OH)) was measured.
It was calculated based on the OH value obtained 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 Production Example 1.

-Production Example 12-In Production Example 2, the types and amounts of the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c), the initial amount of the compound (a) charged and the polymerization thereof. In the same manner as in Production Example 2 except that the temperatures were as shown in Table 3 below,
Polymer [12] was obtained.

The number average molecular weight of the obtained polymer [12] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
The average number of terminal hydroxyl groups (Fn (OH)) was determined according to JIS-K-1.
It was calculated based on the OH value obtained according to 557 and the value of the number average molecular weight measured above. The results are shown in Production Example 1
The results are shown in Table 6 below together with the conversion obtained in the same manner as in the above.

-Production Examples 13 to 15-Sumitomo / Sulzer SMX type element (manufactured by Sulzer Co.) and a reaction tube equipped with an outer jacket (inner diameter 4)
2.7mm, length 450mm, number of elements 12, SU
Compound (a), vinyl monomer (b) and initiator (c) were mixed in the ratio shown in Tables 3 and 4 in a tubular reactor in which five S304 tubes (substantially 190 ml in internal volume) were connected. Use a plunger pump to remove 32ml /
Per minute, and a heating medium was flowed into the jacket so that the internal temperature was stabilized at the polymerization temperature shown in Tables 3 and 4, and continuous polymerization was performed. The average residence time was 30 minutes. Then, the same purification method as in Production Example 1 was used to obtain polymers [13] to [15].

The number average molecular weight (Mn) of the purified polymers [13] to [15] was measured by gel permeation chromatography (G).
PC) and the average number of terminal hydroxyl groups (Fn (OH)) was determined according to JIS.
Calculated based on the OH value obtained according to -K-1557 and the value of the number average molecular weight measured above. Those results,
The polymerization rates obtained in the same manner as in Production Example 1 are shown in Table 6 below.

-Production Example 16- In Production Example 13, the types, ratios and polymerization temperatures of the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c) were as shown in Table 4, The vinyl monomer (b) and the radical polymerization initiator (c) were added in an amount of 30% by a plunger pump immediately before the third reaction tube at 6.4 ml /
A polymer [16] was obtained in the same manner as in Production Example 13 except that the polymer was supplied at a flow rate of minutes.

The number average molecular weight (Mn) of the polymer [16] after purification was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and the average number of terminal hydroxyl groups (Fn (OH)) was calculated. JIS-K-1
It was calculated based on the OH value obtained according to 557 and the value of the number average molecular weight measured above. The results are shown in Production Example 1
The results are shown in Table 6 below together with the conversion obtained in the same manner as in the above.

-Manufacturing Examples 17 and 18-A twin-screw extruder with an outer jacket (inner diameter 1 inch, L / D = 48, barrel number 8, screw SACM645, shaft SNC
M439, SACM645) and a mixture of the compound (a), vinyl monomer (b) and initiator (c) in the ratios shown in Table 4 at a rate of 20 ml / min using a plunger pump. The screw is continuously supplied at a flow rate of, and the shape and rotation number of the screw are determined so that the average residence time in a steady state is about 30 minutes. A heating medium was flowed to perform continuous polymerization.

The number average molecular weight (Mn) of the purified polymers [17] and [18] was measured by gel permeation chromatography (G).
PC) and the average number of terminal hydroxyl groups (Fn (OH)) was determined according to JIS.
Calculated based on the OH value obtained according to -K-1557 and the value of the number average molecular weight measured above. Those results,
The polymerization rates obtained in the same manner as in Production Example 1 are shown in Table 7.

Production Example 19 In Production Example 17, the types and ratios of the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c) and the polymerization temperature are as shown in Table 4, 50% of the vinyl-based monomer (b) and the radical polymerization initiator (c) were added to the raw material supply port at the center of the extruder by a plunger pump to give ml /
A polymer [19] was obtained in the same manner as in Production Example 17 except that the polymer was continuously fed at a flow rate of minutes.

The number average molecular weight (Mn) of the polymer [19] after purification was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and the average number of terminal hydroxyl groups (Fn (OH)) was measured. JIS-K-1
It was calculated based on the OH value obtained according to 557 and the value of the number average molecular weight measured above. The results are shown in Production Example 1
The results are shown in Table 7 below together with the conversion obtained in the same manner as in the above.

-Production Examples 20 to 22-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), the mixture of the compound (a), the vinyl monomer (b) and the initiator (c) in the ratios shown in Table 5 are continuously mixed at a flow rate of 20 ml / min using a plunger pump. Supplied, the paddle speed was 20 rpm, and the average residence time in the steady state was 3
At 0 minutes, a heating medium was flowed into the jacket so that the internal temperature was stabilized at the polymerization temperature shown in Table 5, and continuous polymerization was performed.

The number average molecular weight (Mn) of the purified polymers [20] to [22] was measured by gel permeation chromatography (G).
PC) and the average number of terminal hydroxyl groups (Fn (OH)) was determined according to JIS.
Calculated based on the OH value obtained according to -K-1557 and the value of the number average molecular weight measured above. Those results,
The polymerization rates obtained in the same manner as in Production Example 1 are shown in Table 7.

-Preparation Example 23- In Preparation Example 7, 20 parts (3% by weight of the whole) of dioxane was added to the compound (a) as a component other than the compound (a), the vinyl monomer (b) and the initiator (c). Example 7 except that the initial charge was made in the flask together with
In the same manner as in the above, a polymer [23] was obtained.

The number average molecular weight (Mn) of the purified polymer [23] was measured by a vapor pressure molecular weight measuring device (VPO), and the average number of terminal hydroxyl groups (Fn (OH)) was
It was calculated based on the OH value obtained according to JIS-K-1557 and the value of the number average molecular weight measured above. The results are shown in Table 7 together with the polymerization rates obtained in the same manner as in Production Example 1.
It was shown to.

-Comparative Production Example 1-In Production Example 1, the amount of AIBN was 4.1 parts (compound (a) / initiator (c) = 40 (molar ratio) in the charged composition).
Comparative Polymer (1) was obtained in the same manner as in Production Example 1 except that. In addition, from the residual rate of 2-hydroxyethyl disulfide measured by liquid chromatography and the residual rate of AIBN calculated from the decomposition rate of AIBN at the polymerization temperature of this comparative production example, the compound (a) in the flask at the initial stage of the polymerization was determined. To initiator (c) molar ratio (= (a) / (c))
Was found to be less than 50.

The number average molecular weight and the average number of terminal hydroxyl groups (Fn (OH)) of the obtained comparative polymer (1) were measured in Production Example 1
The number average molecular weight was 2300 and the average number of terminal hydroxyl groups (Fn (OH) 1.2 was obtained in the same manner as described above.)-Comparative Production Example 2-In Production Example 14, the amount of AIBN was 32.8. Comparative polymer (2) was obtained in the same manner as in Production Example 14 except that parts (compound (a) / initiator (c) = 5 (molar ratio)) were used.

A calculated from the residual rate of 2-hydroxyethyl disulfide measured by liquid chromatography and the decomposition rate of AIBN at the polymerization temperature in this comparative production example.
From the residual ratio of IBN, the molar ratio of the compound (a) to the initiator (c) in the flask (=
It was confirmed that (a) / (c)) was far below 50.

The number average molecular weight and the average number of terminal hydroxyl groups (Fn (OH)) of the obtained comparative polymer (2) were measured in Production Example 1
As a result, the number average molecular weight was 2,000 and the average number of terminal hydroxyl groups (Fn (OH)) was 0.8. —Comparative Production Example 3—Comparative Production Example 18 was repeated except that the amount of AIBN was changed to 32.8 parts (compound (a) / initiator (c) = 5 (molar ratio)). Polymer (3) for use was obtained.

A calculated from the residual ratio of 2-hydroxyethyl disulfide measured by liquid chromatography and the decomposition rate of AIBN at the polymerization temperature in this comparative production example.
From the residual ratio of IBN, the molar ratio of the compound (a) to the initiator (c) in the flask (=
It was confirmed that (a) / (c)) was far below 50.

The number average molecular weight and the average number of terminal hydroxyl groups (Fn (OH)) of the obtained comparative polymer (3) were measured in Production Example 1
As a result, the number average molecular weight was 2400 and the average number of terminal hydroxyl groups (Fn (OH)) was 0.7. -Comparative Production Example 4- In Production Example 1, 100 parts of dioxane as a solvent, in addition to the compound (a), the vinyl-based monomer (b) and the radical polymerization initiator (c), the compound (a) and the vinyl-based monomer In the same manner as in Production Example 1 except that initial charging was performed in a flask together with the body (b) and the radical polymerization initiator (c),
A comparative polymer (4) was obtained.

The number average molecular weight and the average number of terminal hydroxyl groups (Fn (OH)) of the obtained comparative polymer (4) were measured in Production Example 1
As a result, the number average molecular weight was 2200 and the average number of terminal hydroxyl groups (Fn (OH)) was 1.0. -Comparative Production Example 5- In Production Example 14, 100 parts of dioxane as a solvent other than the compound (a), the vinyl-based monomer (b) and the radical polymerization initiator (c), the compound (a), and the vinyl-based monomer A comparative polymer (5) was obtained in the same manner as in Production Example 14 except that the mixture obtained by batch-mixing with the body (b) and the radical polymerization initiator (c) was continuously supplied to the reactor.

The number average molecular weight and the average number of terminal hydroxyl groups (Fn (OH)) of the obtained comparative polymer (5) were measured in Production Example 1
As a result, the number average molecular weight was 4800 and the average number of terminal hydroxyl groups (Fn (OH)) was 1.1. -Preparation Example 24-In Preparation Example 1, the amounts of 2-hydroxyethyl disulfide and AIBN were 19.2 parts and 0.1, respectively.
(Compound (a) / vinyl monomer (b) = 0.
Polymer (24) was obtained in the same manner as in Production Example 1 except for 3 (wt ratio).

The number average molecular weight and the average number of terminal hydroxyl groups (Fn (OH)) of the obtained polymer [24] were determined in the same manner as in Production Example 1. The number average molecular weight was 23,000 and the average number of terminal hydroxyl groups (Fn (OH The result was OH)) 1.3. -Example 25- The polymer [1] 100 obtained in Production Example 1 was placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser.
Parts, hexamethylene diisocyanate 8.8 parts (NCO
/OH=1.05 (molar ratio)), 200 parts of toluene and 0.1 part of dibutyltin dilaurate were charged at 80 ° C.
The reaction was completed by stirring for 5 hours with polyurethane [2
5] was obtained.

The number average molecular weight (Mn) of this polyurethane [25] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 8000. -Example 26-In Example 25, 65 parts of polymer [1] and 35 parts of the polymer [2] obtained in Production Example 2 were used in place of 100 parts of the polymer [1], and hexamethylene diisocyanate was added. The same operation as in Example 25 was carried out except that the amount was adjusted to 8.5 parts to obtain a toluene solution of polyurethane [26].

The number average molecular weight (Mn) of this polyurethane [26] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 8000. —Example 27— Example 25 is repeated except that, in Example 25, 50 parts of the polymer [1] and 50 parts of the polymer [2] obtained in Production Example 2 are used instead of 100 parts of the polymer [1]. The same operation as above was performed to obtain a toluene solution of polyurethane [27].

The number average molecular weight (Mn) of this polyurethane [27] was measured by the standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 8000. -Example 28-In Example 27, it replaces with 50 parts of polymers [2],
The procedure of Example 27 was repeated except that 37 parts of the polymer [3] obtained in Production Example 3 was used, and polyurethane [28] was used.
A toluene solution of was obtained.

The number average molecular weight (Mn) of this polyurethane [28] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 1,000. —Example 29— The same operation as in Example 25 except that 70 parts of the polymer [1] and 0.51 part of 1,4-butanediol were used in place of 100 parts of the polymer [1] in Example 25. Then, a toluene solution of polyurethane [29] was obtained.

The number average molecular weight (Mn) of this polyurethane [29] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 1,000. -Example 30- In a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, a dropping funnel and a reflux condenser, methyl ethyl ketone 100 was added.
And 2.0 parts of hexamethylene diisocyanate, and the mixture was 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 0.1 parts of tin dilaurate in 200 parts of methyl ethyl ketone
The resulting solution was added dropwise over 1 hour, and the mixture was further stirred at the same temperature for 3 hours to complete the reaction, thereby obtaining a methyl ethyl ketone solution of a polyester having isocyanate groups at both ends.

Next, the polymer [2] 2 obtained in Production Example 2 was used.
A solution prepared by dissolving 2 parts of dibutyltin dilaurate in 100 parts of methyl ethyl ketone was added dropwise to the flask over 1 hour, and the mixture was further stirred at the same temperature for 3 hours to complete the reaction. A solution was obtained. The number average molecular weight (Mn) of the polyurethane [30] was determined by gel permeation chromatography (GP).
It was 12000 when measured by the standard polystyrene conversion method using C).

Considering this number average molecular weight, the polymer [2] is used as the A component, and Byron GK130 is used as the B component.
It is considered that ABA type segment block type polyurethane was produced. -Example 31- 100 parts of toluene and 3.5 parts of hexamethylene diisocyanate were charged into a flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, a dropping funnel and a reflux condenser, and the temperature was raised to 80 ° C, and then there. Polymer [2] 4 obtained in Production Example 2
A solution of 6 parts and 0.1 part of dibutyltin dilaurate dissolved in 100 parts of toluene was added dropwise over 1 hour, and the mixture was further stirred at the same temperature for 3 hours to complete the reaction, thereby obtaining a polymer having isocyanate groups at both ends. A toluene solution of was obtained.

Next, the polymer [1] 4 obtained in Production Example 1 was used.
A solution prepared by dissolving 0 parts and 0.1 parts of dibutyltin dilaurate in 100 parts of toluene was added dropwise to this flask over 1 hour, and the mixture was further stirred at the same temperature for 3 hours to complete the reaction. A solution was obtained. The number average molecular weight (Mn) of this polyurethane [31] was 38,000 as measured by gel permeation chromatography (GPC) using a standard polystyrene conversion method.

-Example 32- In a flask equipped with a stirrer, a thermometer, an azeotropic dehydration tube, and a reflux condenser, 100 parts of the polymer [1] obtained in Production Example 1 and 7.4 parts of phthalic anhydride were prepared. Charge 5 parts of xylene, mix thoroughly, and dehydrate from the azeotropic dehydration tube at 100 ° C for 2 hours, then 160 ° C for 2 hours, and finally 220 ° C for 1 hour.
The reaction was carried out for an hour to obtain a polyester [32].

The number average molecular weight (Mn) of this polyester [32] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
2000. -Example 33- Instead of 100 parts of the polymer [1] in Example 32, 65 parts of the polymer [1] and 35 parts of the polymer [2] obtained in Production Example 2 were used. Polyester [33] was obtained in the same manner as in Example 32 except that the amount was 7.1 parts.

The number average molecular weight (Mn) of this polyester [33] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
0000. -Example 34-In Example 32, 50 parts of the polymer [1] and 50 parts of the polymer [2] obtained in Production Example 2 were used instead of 100 parts of the polymer [1] in Example 32. The same operation as the above was performed to obtain polyester [34].

The number average molecular weight (Mn) of this polyester [34] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 8000. —Example 35— The same operation as in Example 32 except that 65 parts of the polymer [1] and 1.6 parts of 1,4-butanediol were used in place of 100 parts of the polymer [1] in Example 32. Then, polyester [35] was obtained.

The number average molecular weight (Mn) of this polyester [35] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
5000. -Example 36- 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 of Cymer 325 (manufactured by Mitsui Cyanamid Co., Ltd.) as an alkyl ether aminoformaldehyde resin, 0.25 part of paratoluenesulfonic acid as a curing accelerator, rust preventive pigment 30 parts of zinc chromate, 400 parts of cyclohexanone as a solvent, and 50 parts of an acid value titanium were well stirred and mixed, and were subjected to chromate treatment in advance of 0.5 mm.
It was applied to a thick galvanized steel sheet with a bar coater so that the dry film thickness became 5 μm, and baked at 220 ° C. for 1 minute.

Then, after cooling, 100 parts of the polymer [12] obtained in Production Example 12 on the primer coating film, 30 parts of Cymel 325 (manufactured by Mitsui Cyanamid Co., Ltd.) as an alkyl etherified aminoformaldehyde resin, curing acceleration Paratoluene sulfonic acid 0.25 parts, titanium oxide 125 parts, leveling agent MK Conc (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) 0.5 parts, and cyclohexanone 400 parts were thoroughly stirred and mixed with a paint shaker as an agent, and dried. Apply with a bar coater to a film thickness of 25μ, 70 ℃
And then baked at 235 ° C. for 60 seconds to produce a coated steel sheet. And about this coating,
The coin scratch property was evaluated by the following method (1).

Further, without using the acrylic primer resin, the polymer obtained in Production Example 12 was directly applied to a 0.5 mm-thick galvanized steel sheet which had been previously chromated.
2] 100 parts, 30 parts of Cymel 325 (manufactured by Mitsui Cyanamid Co., Ltd.) as an alkyl etherified aminoformaldehyde resin, 0.25 part of paratoluenesulfonic acid, 125 parts of titanium oxide as a hardening accelerator, MK Conk (Kyoeisha Oil & Fats) 0.5 part of Chemical Industry Co., Ltd.)
A mixture of 400 parts of cyclohexanone with good stirring and mixing with a paint shaker was applied using a bar coater so that the dry film thickness became 25 μm, set at 70 ° C. for 10 minutes, and baked at 235 ° C. for 60 seconds to prepare a coated steel sheet. . And this coating film was evaluated in the following (2) to (6). (1) Coin Scratch Property The state of the coated steel sheet was visually determined after strongly scratching the coated steel sheet using a 10-yen coin.

⊚: Does not peel off from the primer base material (steel plate), has good interlayer adhesion between the primer and the topcoat, and only the topcoat undergoes cohesive failure.・ ・ ・: The primer slightly peels off from the base material, but the interlayer adhesion between the primer and the overcoat is good. Δ: The primer does not peel off from the base material, but the interlayer between the primer and the overcoat is poor and the overcoat is easily peeled off.

X: The overcoat is peeled off from the base material together with the primer. Poor adhesion of primer to substrate. XX: The top coat is remarkably peeled off from the substrate together with the primer. (2) Workability (T vent) The coated steel sheet was bent from 4T at 180 degrees to 0T sequentially, and cracks generated in the bent portion were observed and judged with a 15-fold loupe.
For example, if a crack occurs when three copper plates of the same thickness are sandwiched and bent at the bent portion, the workability is T vent 3T.
Therefore, the smaller the number of T vent, the better the workability. (3) Adhesion A cross-cut loose-peel test was performed according to JIS D-0202. (4) Boiling water test The coated steel sheet was immersed in ion-exchanged water, boiled for 8 hours, taken out, and the coating film was observed and judged.

○: No blisters, adhesion 100/100 △: Blister generation ×: Remarkably blistering (5) Touch resistance JIS was obtained by cross-cutting a coated steel sheet with a cutter knife.
After performing a salt spray test for 500 hours according to -K-5400, the cross cut portion was peeled off with a cellophane tape, and evaluated by the peel width. (6) Pencil hardness This was performed according to JIS K-5400 using Mitsubishi Uni pencil.

The test results are summarized in Table 8. The top coat using the polymer (I) obtained by the above production method is not only excellent in adhesion to a primer and is not easily scratched, but it is also flexible and has excellent processability, and has excellent boiling water resistance and touch resistance. It turned out to be excellent. -Comparative Examples 6 and 7-In Example 36, the same operation as in Example 36 was repeated except that the polymer [12] used in the coating material for the top coat was as shown in Table 8, to prepare a coated steel sheet for comparison. Table 8 summarizes the test results of the coating films.

-Example 37- To 100 parts of the polymer [17] obtained in Production Example 17, 3 equivalents of tolylene diisocyanate was added to trimethylolpropane (Coronate L (manufactured by Nippon Polyurethane Co.)). (Hereinafter, abbreviated as Coronate L) was mixed and diluted with ethyl acetate to a 20% solution to obtain an adhesive solution. As an adherend, a 12 μm-thick polyerylene terephthalate film (hereinafter abbreviated as “PET”) and a 50 μm-thick unstretched polypropylene film (hereinafter abbreviated as “CPP”) subjected to corona discharge treatment were used. For lamination, the above adhesive solution was applied to both of them by a dry laminator so as to have a solid content of 3.0 g / m ^2, and after the solvent was volatilized, they were laminated. At that time, the wetting characteristics of the adhesive solution were examined. The obtained laminate film was cut into a test piece having a width of 15 mm, and a T-type peel test was performed at 300 mm / min using a tensile tester.
The initial adhesion was measured. After lamination, 50 ℃
A test piece was prepared from the laminate film obtained by curing for 3 days under the conditions described above, and the normal adhesion, hot water resistance, chemical resistance and flexibility were evaluated by the following methods. Table 9 shows the results. (1) Normal adhesive strength A T-peel tester similar to the initial adhesive strength was used. (2) Hot water resistance, chemical resistance test Hot water resistance, chemical resistance test In the hot water resistance test, a test piece was placed in a 50 cc autoclave together with water, treated at 120 ° C. for 5 hours, then subjected to a T-type peel test, and a peel test was conducted. The condition and strength were examined. In the chemical resistance test, a T-peel test was performed on a test piece immersed in a 4% aqueous acetic acid solution at 25 ° C. for 4 hours. (3) Flexibility Flexibility was determined by the state of peeling in each of the above peeling tests. The meanings of the marks in the table are as follows.

◯: The peel strength is large, and peeling occurs, which indicates uniform strength. Δ: Although the strength is partially high, there are some places where it is easily peeled off. X: The peeling strength is small easily. (4) Wetting characteristics (observation results) ◯: Uniform application is possible Δ: Partially repellent ×: Repellent The adhesive composition using the polymer (I) obtained by the above production method is used as an adhesive for lamination. When used, not only did the adhesive strength in the initial and normal states be strong, but it was also very excellent in hot water resistance, chemical resistance and flexibility.

-Comparative Examples 8 and 9-A test piece of a comparative laminated film was prepared by repeating the same operation as in Example 37 except that the polymer shown in Table 9 was used instead of the polymer [17]. Got Table 9 shows the evaluation results of the normal adhesion, hot water resistance, chemical resistance and flexibility of the test piece.

Example 38 To 35 parts of the polymer [16] obtained in Production Example 16 were added 35 parts of ethyl acetate, 30 parts of toluene, and Coronate L (isocyanate compound manufactured by Nippon Polyurethane Company), and the mixture was stirred well. Then, it was applied on a PET film having a thickness of 25 μm so that the thickness after drying would be 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 (probe tack) and the adhesive holding power were measured by the following methods, and the results shown in Table 10 were obtained. Adhesive force : The pressure-sensitive adhesive sheet (25) was tested in an atmosphere at a temperature of 23 ° C. and a humidity of 65%, and in an atmosphere at a temperature of 5 ° C.
mm width) is bonded to the polyethylene plate by reciprocating a 2 kg rubber roller once. After 25 minutes, the resistance value was measured when the film was peeled off at a speed of 300 mm / min in the direction of 180 degrees.

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. Adhesion holding force : A test pressure-sensitive adhesive sheet was stuck on a stainless steel plate (SUS304) with an area of 25 mm x 25 mm,
After one minute, the time required for falling at 80 ° C. with a load of 1 kg was measured.

Polymer (I) obtained by the above production method
The pressure-sensitive adhesive composition using was excellent not only in adhesive strength at room temperature, probe tack and adhesive holding power, but also in adhesive strength and probe tack especially at low temperature. -Example 39-In Example 38, the same operation as in Example 38 was repeated except that the polymer [7] obtained in Production Example 7 was used in place of 35 parts of the polymer [16], and pressure-sensitive adhesion was performed. Got the sheet.

With respect to this pressure-sensitive adhesive sheet, the adhesive force at 23 ° C. and 5 ° C., the initial tack and the adhesive holding force were measured by the methods described above, and the results shown in Table 10 were obtained. -Comparative Example 10-A pressure-sensitive adhesive sheet for comparison was obtained by repeating the same operation as in Example 38 except that the polymer shown in Table 10 was used instead of 35 parts of the polymer [16].

With respect to this pressure-sensitive adhesive sheet for comparison, the adhesive force at 23 ° C. and 5 ° C., the initial tack and the adhesive holding force were measured by the methods described above, and the results shown in Table 10 were obtained. -Example 40- 100 parts of the polymer [13] obtained in Production Example 13 and 100 parts of calcium carbonate, 15 parts of titanium dioxide, 20 parts of calcium oxide, and Disparlon 3600N (Kusumoto Kasei Co., Ltd.)
2 parts), 0.5 parts of dibutyltin dilaurate and 0.2 parts of carbon black were sufficiently stirred with a kneader, and 9.5 parts of hexamethylene diisocyanate was added.
An elastic sealant was obtained by thoroughly stirring at 80 ° C. for 3 hours in a kneader. JIS-A for the elastic sealant
When the property evaluation by 5557 and the weather resistance test shown below were performed, the results shown in Table 11 were obtained. (1) Weather resistance test A test piece (dumbbell) prepared beforehand was allowed to stand still on a sunshine weather meter under the conditions of 63 ° C. in atmospheric temperature, UV irradiation, rain for one cycle for 2 hours, and rain for 18 minutes in one 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 from the ratio of the maximum elongation before and after the weather resistance test. Table 11 shows the results.

Polymer (I) obtained by the above production method
The elastic sealant composition using No. 1 was excellent not only in elongation under normal conditions but also in weather resistance. -Example 41-In place of the polymer [13] in Example 40, Production Example 5
The same operation as in Example 40 was repeated except that the polymer [5] obtained in step 1 was used to obtain an elastic sealant. When the characteristics of this elastic sealant were evaluated in accordance with JIS-A5757, the results shown in Table 11 were obtained.

Comparative Examples 11 to 13 The same operation as in Example 40 was repeated except that the polymer shown in Table 11 was used instead of the polymer [13] in Example 40 to obtain a comparative elastic sealant. When the characteristics of this comparative elastic sealant were evaluated in accordance with JIS-A5757, the results shown in Table 11 were obtained.

Example 42 A mixture of 700 parts of the polymer [1] obtained in Preparation 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. . The dried and degassed polyol mixture is treated with Isonate
143-L (Upjohn Polymer Chem)
365 parts (2.56 meq / g of isocyanate). This temperature was maintained at 70 ° C. for 70 minutes to complete the reaction. This product has 2.2 meq / g
Isocyanate content and 20,000 cp at 25 ° C
An almost colorless liquid having a viscosity of s. After storing the sample at 80 ° C. for 2 weeks, the product
The viscosity increased to 000 cps. Product 8 heated to 35 ° C.
0 g of a 100% 2% aqueous solution of Pluronic L-62, a nonionic surfactant from Wyandotte,
The mixture was stirred vigorously with 1 to obtain a soft, supple, flexible urethane foam. Table 12 shows the physical properties.

-Comparative Examples 14 to 16-In Example 42, the same operation as in Example 42 was repeated except that the polymer of the kind and amount shown in Table 12 was used instead of 700 parts of the polymer [1] for comparison. A flexible urethane foam for use was obtained. The physical properties are shown in Table 12. -Reference Example 43- (Synthesis of Polymer Having Polymerizable Unsaturated Groups at Both Terminals) 100 parts of polymer [21] obtained in Reference Example 21 in a flask equipped with a stirrer, a reflux condenser and a thermometer, anhydrous Charge 5.6 parts of maleic acid, 0.1 part of dibutyltin oxide, 0.1 part of hydroquinone and 200 parts of toluene, 1
After stirring at 00 ° C. for 5 hours to carry out the reaction, toluene was removed by an evaporator and a reduced pressure dryer, and the polymer [4
3] was obtained.

-Reference Example 44- (Synthesis of Polymer Having Polymerizable Unsaturated Groups at Both Terminals and Side Chains) The polymer obtained in Production Example 22 was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. 22] 100 parts, 2-isocyanatoethyl methacrylate 11 parts, dibutyltin dilaurate 0.1 part, hydroquinone 0.1 part and toluene 200 parts were charged, and the mixture was stirred at 80 ° C. for 5 hours to carry out a reaction, and then an evaporator. Then, toluene was removed by a vacuum dryer to obtain a polymer [44].

-Reference Examples 45 to 49- Using the polymers [43] and [44] obtained in Reference Examples 43 and 44, gel coat resin compositions were prepared in the formulations and amounts shown in Table 13. 2.5 parts of Aerosil 200 (Thixotropic agent, manufactured by Nippon Aerosil Co., Ltd.), 0.015 part as a metal component of cobalt naphthenate, and 55% methyl ethyl ketone peroxide (Permelic N, Japan) (Made by Yushi) 1.0
After adding and mixing well, a spray gun having a diameter of 3.0 mm was used to apply an air pressure of 3.0 Kg / cm ^{2 to} obtain a coating film thickness of 0.1 kg / cm ² .
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, and then allowed to cool to room temperature, and a glass fiber reinforced plastic layer was molded and cured on the obtained coating film using an unsaturated polyester resin and glass fiber. Thereafter, the molded product was removed 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 has no sagging when applied to various molded articles, and has a low viscosity at the time of work and good workability, as well as a high hardness, and can form a gel coat layer having good weather resistance. all right. (1) Viscosity, thixotropic degree and gel time This was carried out in accordance with JIS6901 Liquid Unsaturated Polyester Resin Test Method. (2) Film forming property The appearance (repelling) at the time of spray coating was visually judged. (3) Pencil hardness The pencil hardness was measured according to JIS K-5400 using Mitsubishi Uni pencil. (4) Weather resistance (blister generation time) Using a sunshine weatherometer manufactured by Suga Test Machine, an atmosphere temperature of 65 ° C, a spray cycle of 18 minutes / 120 minutes, and a light source: arc carbon were used to form one sample molded product.
The gloss of the surface gel coat layer after 60 hours (60
(゜ Gloss) retention.

Reference Example 50 The polyurethane [26] obtained in Example 26 was evaluated for the following thermoplastic elastomers.
Table 14 shows the results. (1) Tensile elongation test It was carried out according to JIS K 6301 using a No. 3 dumbbell. (2) Oil resistance test The polymer was immersed in JIS # 3 oil at 100 ° C for 70 hours, and the volume change (%) of the polymer after immersion with respect to before the test was measured. (3) Weather resistance test In a sunshine weather meter, a dumbbell melt-cast at 200 ° C and molded at 200 ° C under an atmosphere temperature of 63 ° C and a UV irradiation for one cycle for 2 hours and a rainfall of 18 minutes during one cycle was allowed to stand. After 24 hours and 330
After a while, remove the dumbbell and save its elongation (%)
Was measured. The elongation preservation rate was determined by measuring the tensile elongation at break according to JIS K 6301 and determining the ratio before and after the weather resistance test. (4) Chemical resistance test A test was performed using No. 3 dumbbell according to JIS K6301. After immersing the polymer in a 40% aqueous NaOH solution and each solvent at 23 ° C. for 5 days, the polymer was taken out and its surface state was observed. The chemical resistance was graded from A to D from the surface state.

A: No change at all B: Almost no change C: Surface slightly swelled D: Becomes brittle when expanded Thermoplastic elastomers using polyurethane and polyester not only have large elongation in the normal state, but also oil resistance It was also excellent in weather resistance and chemical resistance.

-Reference Example 51- In Reference Example 50, the same evaluation was carried out by using the polyurethane [31] obtained in Example 31 instead of the polyurethane [26] obtained in Example 26. Table 14 shows the obtained results. -Reference Example 52- In Reference Example 50, the same evaluation was performed using the polyester [33] obtained in Reference Example 33 instead of the polyurethane [26] obtained in Example 26. Table 14 shows the obtained results.

-Comparative Reference Examples 17 and 18-The same operations as in Reference Example 50 were repeated except that the polymers shown in Table 14 were used in place of the polyurethane [26] obtained in Example 26 in Reference Example 50. An evaluation test was performed on the thermoplastic elastomer of the comparative polymer. The results are shown in Table 14.

Reference Examples 53 and 54 The polyurethane [27] obtained in Example 27 and the polyester [34] obtained in Reference Example 34 were evaluated for the following molding materials, and the results are shown in Table 15. Summarized. (1) Molding processability The temperature dependence of the melt flow characteristics of polyurethane and polyester was measured by using a temperature rise method (Hold 18) using a Koka type flow tester.
The viscosity was measured at 5 ° C. × 5 min, heating rate 5 ° C./min, die diameter × length = 0.5 mmφ × 5 mmL, load 20 kg), and the activation energy Ea of apparent melt flow was measured.
(Kcal / mol) plots the logarithmic value of the flow ratio correlated with the absolute temperature against the reciprocal of the absolute temperature,
The slope K was obtained and calculated by the following equation.

Ea = −2.303 R · K (where R represents a gas constant (1.987 cal / deg · mol)) (2) Low temperature property Regarding the low temperature property, the obtained polyurethane (polyester) pellets were heated at 250 ° C. Pressurize for 2 minutes (10kg / cm
² ) Press to prepare a 100μ film,
The evaluation was performed by measuring the main dispersion peak temperature (Ta) using a dynamic viscoelasticity automatic measuring machine (110 Hz). (3) Hydrolysis resistance The hydrolysis resistance was evaluated by a jungle test. In the jungle test, a polyurethane (polyester) film having a thickness of 50 μm was left at 70 ° C. and a relative humidity of 95% for 30 days, and the tensile strength retention of the film before and after the jungle test was evaluated. (4) Weather resistance test In a weather meter, the atmosphere condition was set to 40 ° C. and the humidity was 68%, and a polyurethane (ester) film having a thickness of 50 μ was irradiated with light. After 7 days, the polyurethane (ester) film was taken out. The tensile strength preservation rate (%) before and after the weather resistance test was measured.

The molding materials using polyurethane and polyester had good molding workability and were excellent not only in low temperature characteristics but also in hydrolysis resistance and weather resistance. -Comparative Reference Examples 19 and 20-In Reference Example 53, the polymer shown in Table 15 was used instead of the polyurethane [27] obtained in Example 27, and an evaluation test was conducted on the above molding material. It is summarized in Table 15.

[0178]

[Table 1]

[0179]

[Table 2]

[0180]

[Table 3]

[0181]

[Table 4]

[0182]

[Table 5]

[0183]

[Table 6]

[0184]

[Table 7]

The notes to Tables 6 and 7 above are as follows: * 1: Calculated from the nonvolatile content of the polymerization solution after the 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 using standard polystyrene. However, the numerical value in parentheses is the ratio (Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
w / Mn). * 3: The average number of terminal hydroxyl groups (Fn (OH)) is based on JIS-
It was calculated based on the OH value obtained according to K-1557 and the value of the number average molecular weight measured in * 2 above. * 4: First, the obtained polymer and Sumidur N-75
(A trifunctional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd.) so that the molar ratio of isocyanate groups to hydroxyl groups becomes 1.1 / 1 to obtain a toluene solution of about 40%. A small amount of tin dilaurate was added and mixed well with stirring to react at 80 ° C. for 3 hours to obtain a polyurethane film. Next, after sufficiently drying the film, it was subjected to Soxhlet extraction using tetrahydrofuran as a solvent for 8 hours, and the weight% of the insoluble portion remaining without extraction was indicated as a gel fraction.

[0186]

[Table 8]

[0187]

[Table 9]

[0188]

[Table 10]

[0189]

[Table 11]

[0190]

[Table 12]

[0191]

[Table 13]

[0192]

[Table 14]

[0193]

[Table 15]

Example 55 The polymer [1] 100 obtained in Production Example 1 was placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser.
Parts, 1,4-butanediol 10 parts, TDI was NCO /
OH = 1.05 (molar ratio), and 0.1 part of dibutyltin dilaurate was charged.
The reaction was completed by continuing stirring at 5 ° C. for 5 hours to obtain polyurethane [55].

The number average molecular weight (Mn) of this polyurethane [55] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
It was 39,000. This polyurethane [55] is
Redissolved in HF to form a film. -Comparative Example 21-In Example 55, the same operation as in Example 55 was repeated except that a conventionally known polyester polyol having a number average molecular weight (Mn) of 2,000 was used in place of the polymer [1], and for comparison, Polyurethane [21] was obtained.

Comparative Example 22 The same operation as in Example 55 is repeated except that a conventionally known polyether polyol having a number average molecular weight (Mn) of 3,000 is used in place of the polymer [1]. Thus, a comparative polyurethane [22] was obtained. -Example 56 and Comparative Examples 23 to 24-Polyurethane [55] obtained in Example 55 and comparative polyurethane [21] obtained in Comparative Examples 21 to 22-
For [22], the following evaluation tests were performed on artificial leather and synthetic leather. (1) Hydrolysis-resistant polyurethane [55] and comparative polyurethane [2
1] was evaluated by a jungle test. In the jungle test, a polyurethane film having a thickness of 50 μm was allowed to stand at 70 ° C. and 95% relative humidity for 12 days, and the tensile strength retention of the film was evaluated based on the results of stress-strain characteristics by Instron before and after the jungle test. The results were as follows.

Sample Tensile strength retention rate Polyurethane [55] 100% Comparative polyurethane [21] 80% (2) Heat resistance The heat resistance of polyurethane [55] and comparative polyurethane [22] was evaluated. The heat resistance of urethane film is 12
The film was allowed to stand under hot air drying at 0 ° C. for about 6 days, and the film was evaluated for tensile strength retention from the results of stress-strain characteristics by Instron before and after hot air drying.

Sample Tensile Strength Retention Rate Polyurethane [55] 100% Comparative Polyurethane [22] The shape of the film was not retained. -Example 57- 760 parts of the polymer [4] obtained in Production Example 4 and 66.7 parts of isophorone diisocyanate were mixed in a flask equipped with a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser, and 9
The reaction was carried out at 5 ° C. for 10 hours to obtain a urethane prepolymer having 1.5% free NCO. Next, 620 parts of methyl ethyl ketone (MEK) was added to make a uniform solution, and then a solution prepared by dissolving 23.3 parts of isophoronediamine and 2.4 parts of di-n-butylamine in a mixed solution of 226 parts of MEK and 118 parts of isopropanol was added. Then, 1447 parts of a MEK solution of the urethane prepolymer was added dropwise at room temperature. After dripping,
The temperature was raised and the reaction was carried out at 50 ° C. for 3 hours.

Next, 25 parts of titanium oxide, 37.5 parts of the polyurethane solution (polymer concentration 47%), and ME.
23 parts of K was placed in a ball mill for 24 hours, and then 29 parts of ethyl acetate was added to obtain a printing ink composition. Using this ink composition, a gravure printing machine is used to print on a nylon film and a polyester film, and printability (adhesion and blocking resistance) and durability (hydrolysis resistance and heat deterioration resistance) are determined by the methods described below. Was examined. Table 16 shows the results. This printing ink composition did not change in viscosity even after long-term storage, and had good dispersibility. (1) Printability Adhesiveness (cellophane tape adhesiveness) After printing, leave it for one day, apply cellophane tape to the printed part, and quickly peel it off.

Good: No peeling at all. Bad: Partially peeled. Blocking resistance The printed surfaces of the two printed materials are combined and the two printed surfaces are stacked and fastened by a hot press so that the printed surfaces are in close contact.
After leaving for a while, the printed matter was peeled off.

Good: Peeled without any feeling of resistance. Slightly good: There is very little resistance. Poor: Those with obvious resistance or those that do not peel off. (2) Durability Hydrolysis resistance The printed matter was immersed in hot water at 100 ° C. for 72 hours, and the adhesion of the printed portion was examined.

Good: No tackiness. Bad: sticky. Heat-Resistant Degradation After the printed matter was left in a hot-air dryer at 120 ° C. for one week, the adhesiveness of the printed portion was examined.

Good: No tackiness. Bad: sticky. -Comparative Example 25-In Example 57, the same operation as in Example 57 was repeated except that 300 parts of polytetramethylene glycol having a conventionally known number average molecular weight (Mn) of 2,000 was used in place of the polymer [4]. A printing ink composition for comparison made of polytetramethylene glycol was obtained, and the printability and durability of this composition were examined by the same method as in Example 57. Table 16 shows the results.

Comparative Example 26 In Example 57, 300 parts of a conventionally known polybutylene adipate diol having a number average molecular weight (Mn) of 2,000 and 4,4-dicyclohexylmethane diisocyanate were used in place of the polymer [4]. The same operation as in Example 57 was repeated except that 79 parts were used to obtain a comparative printing ink composition made of polytetramethylene glycol. This composition was subjected to the same method as in Example 57 for printability and durability. I investigated the sex. Table 16 shows the results.

[0205]

[Table 16]

-Production Example 58- (Production Example for Thermosetting Polyurethane Elastomer Composition) The same operation as in Production Example 1 except that 43 parts of methyl acrylate was used in place of 64 parts of butyl acrylate in Production Example 1. The number average molecular weight of 2,200,
A polymer [58] having Fn (OH) = 2.0 was obtained.

Example 59-Example of Thermosetting Polyurethane Elastomer Composition In a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 1200 parts of the above polymer [58],
51 parts of butanediol and 397 parts of TDI were charged and reacted in a nitrogen stream at 80 ° C. for 3 hours with stirring.

1660 parts of the obtained reaction product was degassed under reduced pressure at 80 ° C. and previously dissolved at 120 ° C.
284 parts of 3'-dichloro-4,4'-diaminodiphenylmethane was added, and the mixture was stirred for 1 minute so as not to involve bubbles, poured into a mold heated to 100 ° C and cured at 100 ° C for 24 hours to obtain a polyurethane elastomer [5.
9].

The stress-strain characteristic (by Instron) and durability of this polyurethane elastomer [59] were examined.
The durability was evaluated based on the following hydrolysis resistance and heat resistance. Table 17 shows the results. (1) Hydrolysis resistance It was evaluated by a jungle test. In the jungle test, the polyurethane molded product was allowed to stand at 70 ° C. and 95% relative humidity for 12 days, and the tensile strength retention of the molded product was evaluated from the results of stress-strain characteristics by Instron before and after the jungle test. (2) Heat resistance The urethane film was allowed to stand under hot air drying at 120 ° C. for about 6 days, and the tensile strength retention of the film was evaluated from the results of stress-strain characteristics by Instron before and after hot air drying.

Comparative Example 27- (Comparative Example Concerning Thermosetting Polyurethane Elastomer Composition) In Example 59, a conventionally known polyester polyol having a number average molecular weight (Mn) of 1,000 is used in place of the polymer [58]. The same operation as in Example 59 was repeated except that 552 parts was used to obtain a comparative polyurethane elastomer [27].

This comparative polyurethane elastomer [2
The stress-strain characteristics and durability of [7] were examined in the same manner as in Example 59. Table 17 shows the results. -Comparative Example 28- (Comparative Example for Thermosetting Polyurethane Elastomer Composition) In Example 59, 552 parts of a conventionally known polyether polyol having a number average molecular weight (Mn) of 1,000 was used in place of the polymer [58]. The same operation as in Example 59 was repeated except that it was used to obtain a comparative polyurethane elastomer [28].

This comparative polyurethane elastomer [2
The stress strain characteristic and the durability of [8] were examined in the same manner as in Example 59. Table 17 shows the results.

[0213]

[Table 17]

-Example 60- (Example relating to resin composition for flooring material) In a flask equipped with a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser, 85 parts of the polymer [1] of Production Example 1 and TDI8 were added. Put 3 parts,
The mixture was reacted in a nitrogen stream at 80 ° C. for 3 hours with stirring to obtain a polymer [1] / TDI prepolymer.

Next, using this polymer [1] / TDI prepolymer, a polyurethane composition (resin composition for flooring materials) having the composition shown in Table 18 was produced.
Measures surface adhesion and durability (hydrolysis resistance and heat resistance)
evaluated. Table 19 shows the results. -Comparative example 29- (Comparative example regarding resin composition for flooring materials) A polypropylene glycol 85 having a number average molecular weight of 2,000 was placed in a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser.
Parts and 15 parts of TDI, and put in a nitrogen stream at 80 ° C for 3
The reaction was carried out with stirring for a time to obtain a polypropylene glycol / TDI prepolymer.

Next, this polypropylene glycol / T
Using a DI prepolymer, a comparative polyurethane composition (flooring resin composition) having the composition shown in Table 18 was produced, and the hardness, surface tackiness, and durability (hydrolysis resistance and heat resistance) were determined. Measured and evaluated. Table 19 shows the results. -Comparative Example 30- In a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 85 parts of a polyester polyol having a number average molecular weight of 2,000 and 15 parts of TDI were placed, and the mixture was heated to 3 at 80 ° C in a nitrogen stream. The reaction was carried out with stirring for a time to obtain a polyester polyol / TDI prepolymer.

Next, this polyester polyol / TD
Using I prepolymer, a comparative polyurethane composition (flooring resin composition) having the composition shown in Table 18 was produced, and the hardness, surface tackiness, and durability (hydrolysis resistance and heat resistance) were measured. Measured and evaluated. Table 19 shows the results.

[0218]

[Table 18]

[0219]

[Table 19]

Reference Example 61- (Synthesis of Polymer Having Polymerizable Unsaturated Groups at Both Terminals) In Reference Example 43, except that 116 parts of the polymer [1] is used instead of 100 parts of the polymer [21]. The same operation as in Reference Example 43 was repeated to obtain a polymer [61]. -Reference Example 62- (Synthesis of Polymer Having Polymerizable Unsaturated Groups at Both Terminals) Reference Example 43 except that 116 parts of the polymer [2] is used in place of 100 parts of the polymer [21] in Reference Example 43. The same operation as above was repeated to obtain a polymer [62].

Reference Example 63- (Synthesis of a Polymer Having Polymerizable Unsaturated Groups at Both Terminals) In Reference Example 43, except that 452 parts of the polymer [6] is used instead of 100 parts of the polymer [21]. The same operation as in Reference Example 43 was repeated to obtain a polymer [63]. -Reference Example 64-(Synthesis of Polymer Having Polymerizable Unsaturated Groups at Both Terminals) Reference Example 43 except that 65 parts of the polymer [10] is used in place of 100 parts of the polymer [21] in Reference Example 43. The same operation as above was repeated to obtain a polymer [64].

-Reference Example 65- 50 parts of the polymer [62] obtained in Reference Example 62, 48.5 parts of styrene, a silane coupling agent (KBM-503,
1.5 parts of Shin-Etsu Chemical Co., Ltd.) were mixed to obtain a resin composition. Next, 200 parts of aluminum hydroxide (Heidilite H-320, average particle size 3.5 microns, manufactured by Showa Denko KK) was kneaded into the resin composition using a high-speed stirrer.
Subsequently, 0.8 part of Kayaester O (t-butylperoxy-2-ethylhexanoate, manufactured by Kayaku Nuuri Co., Ltd.) was added as a curing agent, mixed, and defoamed under reduced pressure to obtain a compound. Was. The viscosity of this formulation was 7 poise at a liquid temperature of 30 ° C.

This composition was poured into a casting mold of 1000 × 600 × 6 mm and cured at 60 ° C., and it was cured in 30 minutes, and post-cured at 120 ° C. for 2 hours.
The obtained cured product has a marble-like appearance that scatters light beautifully in a milky white color, has flame retardancy, and has excellent impact resistance and machinability as shown in Table 21. Met.

-Reference Examples 66 to 69-Cured products were obtained by performing the same operations as in Reference Example 65 except that the compounding composition was as shown in Table 20. These cured products are
It scattered milky white light, had flame retardancy, and was excellent in impact resistance and cutting workability as shown in Table 21. -Comparative Reference Example 31-27 parts of polymethyl methacrylate (Acrypet MD011, manufactured by Mitsubishi Rayon Co., Ltd.) was added to methyl methacrylate 73.
To obtain a methyl methacrylate syrup (resin liquid) having a viscosity of 5 poise.

Next, aluminum hydroxide (Hidiglite H-320, average particle size 3.5 μm,
200 parts of Showa Denko Co., Ltd.) were kneaded using a high-speed stirrer, and then 0.8 parts of Kayaester O (manufactured by Kayaku Nury Co., Ltd.) was added as a curing agent. ,
A comparative resin formulation was obtained. The viscosity of this resin composition is 200 poise at a liquid temperature of 30 ° C., and many bubbles remain.
Casting was difficult due to poor fluidity. This resin composition was poured into a casting mold of 1000 × 600 × 6 mm, and cured at 60 ° C., which was cured in 20 minutes and further cured at 110 ° C. for 2 hours.

As to the physical properties of the obtained cured product, as shown in Table 23, there was a problem in impact resistance. -Comparative Reference Example 32-As shown in Table 22, the same as Example 65 except that 20 parts of ethylene glycol dimethacrylate was used instead of 50 parts of the polymer [62] having a polymerizable unsaturated group at both ends. The operation was performed to obtain a cured product.

The physical properties of the obtained cured product are as shown in Table 23 and were inferior in impact resistance and workability. -Comparative Reference Example 33-30 parts of trimethylolpropane trimethacrylate, 50 parts of styrene, 20 parts of methyl methacrylate, and a 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 (Hydrite H-320, average particle size 3.5 μm,
300 parts of Showa Denko KK were kneaded using a high-speed stirrer, and then Kayaester P-70 (t-
Butyl peroxypivalate, manufactured by Kayaku Nuuri Co., Ltd.)
0.5 part by weight was added, mixed, and then defoamed under reduced pressure to obtain a comparative composition. The viscosity of this formulation was 10 poise at a liquid temperature of 30 ° C.

This formulation is then added to 1000 × 600 × 6.
mm casting mold and cured at 50 ° C,
The composition was cured in 45 minutes and further cured at 120 ° C. for 2 hours. The resulting cured product has a marble-like translucency that scatters light beautifully in milky white, has flame retardancy,
As shown in Table 23, the heat distortion temperature was as high as 230 ° C, but the impact resistance and workability were poor.

Comparative Reference Example 34 Vinyl ester resin (55 parts of bisphenol A type epoxy acrylate resin dissolved in 45 parts of styrene)
Aluminum hydroxide (Heidilite H-320, average particle size of 3 parts) was mixed in a resin liquid in which 1.5 parts of a silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 100 parts.
200 parts (5 microns, 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 Nury Co., Ltd.) was added, mixed, and then defoamed under reduced pressure to obtain a resin composition for comparison.

The viscosity of this resin compound was 3 at a liquid temperature of 30 ° C.
Due to the presence of 00 poise, many bubbles remained and the fluidity was poor, which made casting difficult. This resin compound is
When poured into a 000 × 600 × 6 mm casting mold and cured at 60 ° C., it was cured in 50 minutes and further post-cured at 110 ° C. for 2 hours. Table 23 shows the physical properties of the obtained cured product.
As shown in Table 2, there were problems in impact resistance and workability.

[0232]

[Table 20]

[0233]

[Table 21]

[0234]

[Table 22]

[0235]

[Table 23]

Reference Example 70- (Synthesis of Polymer Having Carboxyl Group at Both Terminals) 100 parts of the polymer [1] obtained in Production Example 1 was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. , Maleic anhydride 5.5 parts, triethylamine 2.8 parts were charged, and the temperature was 80 ° C.
After stirring for 6 hours, a polymer [70] was obtained.

With respect to the physical properties of the polymer [70], the number average molecular weight (Mn) was 3800 as measured by GPC, and the number of terminal carboxyl groups (Fn (COOH)) was 2.0 from the titration with alcoholic KOH and the above number average molecular weight. From this, it is considered that the reaction proceeded quantitatively. -Reference Example 71- (Synthesis of Polymer Having Carboxyl Groups at Both Terminals) A flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 100 parts of the polymer [13] obtained in Production Example 13 and anhydrous amber. Charge 5.0 parts of acid and 2.1 parts of sodium acetate, 80 ℃
After stirring for 6 hours, a polymer [71] was obtained.

With respect to the physical properties of the polymer [71], the number average molecular weight (Mn) was 4100 as measured by GPC, and the number of terminal carboxyl groups (Fn (COOH)) was 2.0 based on the titration with alcoholic KOH and the above number average molecular weight. From this, it is considered that the reaction proceeded quantitatively. -Reference Example 72- (Synthesis of Polymer Having Carboxyl Group at Both Ends) 100 parts of the polymer [14] obtained in Production Example 14 and anhydrous phthalate were placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. Charge 5.9 parts of acid and 2.0 parts of triethylamine.
The mixture was stirred at 0 ° C for 6 hours to obtain a polymer [72].

With respect to the physical properties of the polymer [72], the number average molecular weight (Mn) was 5100 as measured by GPC, and the number of terminal carboxyl groups (Fn (COOH)) was 1.9 as determined by titration with an alcoholic KOH and the number average molecular weight obtained above. From this, it is considered that the reaction proceeded quantitatively. -Reference Example 73- (Synthesis of Polymer Having Carboxyl Group on Both Terminals and Side Chains) 100 parts of the polymer [17] obtained in Production Example 17 was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. ,
0.7 parts of itaconic anhydride and 0.3 parts of triethylamine were charged and stirred at 90 ° C. for 6 hours to obtain a polymer [73].

With respect to the physical properties of the polymer [73], the number average molecular weight (Mn) was 16000 as measured by GPC, and the polymer 1 was determined by titration with an alcoholic KOH and the number average molecular weight obtained above.
The number of carboxyl groups per molecule (Fn (COOH)) was 6.0, indicating that the reaction proceeded quantitatively. -Reference Example 74-The polymer [70] obtained in Reference Example 70 was mixed with the epoxy resin and the curing agent in the ratios shown in Table 24 to obtain an epoxy resin composition.

An adhesive test and a heat resistance test were conducted on this epoxy resin composition. In the adhesion test,
A 1.5 mm thick (0.5 mm T-type peel test) cold rolled steel plate was polished with # 100 sandpaper, washed and degreased with acetone, and heated at 150 ° C. for 1 hour to cure the adhesive. The test was performed by measuring the tensile shearing force and the T-peel strength. The heat resistance test was performed by leaving the sample for the adhesion test under hot air drying at 120 ° C. for about 6 days, and performing an adhesion test before and after the hot air drying to determine the strength retention. The results are shown in Table 24.

Reference Example 75 The same operation as in Reference Example 74 was repeated, except that the polymer [70] obtained in Reference Example 70 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 24. -Comparative Reference Example 35-An adhesion test was performed by repeating the same operation as in Reference Example 74 without using the polymer [70] as the rubber component in Reference Example 74. The results are shown in Table 24.

-Comparative Reference Example 36-In Reference Example 74, instead of using the polymer [70], Hiker CTBN 130 manufactured by Ube Industries as a rubber component.
An adhesion test and a heat resistance test were performed by repeating the same operation as in Reference Example 74 except that 0X8 was used. The results are shown in Table 24. -Comparative Reference Example 37-In Example 75, instead of using the polymer [70], a hiker CTBN130 manufactured by Ube Industries, Ltd. was used as a rubber component.
An adhesion test and a heat resistance test were performed by repeating the same operation as in Reference Example 75 except that 0X8 was used. The results are shown in Table 24.

[0244]

[Table 24]

[0245]

INDUSTRIAL APPLICABILITY In the method for producing a polymer having a hydroxyl group at both ends (polymer (I)), the polymerization of the vinyl monomer (b) is carried out in the presence of the compound (a) by a radical polymerization initiator ( c)
When the compound (a) is always present in the reactor in an amount of 50 mol times or more of the initiator (c) during the reaction, the other components (a), (b) and (c) In order not to use the substance substantially, hydroxyl groups are easily and reliably introduced to both ends of the polymer, and more efficiently,
As a result, the polymer (I) can be obtained easily, inexpensively, and efficiently from a wide range of vinyl monomers including polar vinyl monomers.

The polymer (I) obtained by this production method has a hydroxyl group at both ends, so that it has various resins such as polyester resin, polyurethane resin and polycarbonate resin, various block polymers, paints and elastic walls. Materials, waterproof membranes, floor materials, adhesives, tackifiers, adhesives, binders, sealing materials, urethane foam (hard, semi-hard, soft), urethane RIM, UV
EB curing resin, high solid paint, thermosetting elastomer, thermoplastic elastomer, microcellular, artificial leather, synthetic leather, elastic fiber, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coating agent, Resin for artificial marble, impact modifier for artificial marble, resin for ink,
As raw materials for films (lamination adhesives, protective films, etc.), laminated glass resins, reactive diluents,
It is very useful as various resin additives and raw materials thereof, and by reacting hydroxyl groups at both ends by an appropriate method, a functional group other than a hydroxyl group (for example, a polymerizable unsaturated group such as a vinyl group, 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.) can be easily converted to a polymer having both ends. This polymer is also very useful.
For example, a polymer having carboxyl groups at both ends 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 terminal hydroxyl groups of a polymer having hydroxyl groups at both ends, it becomes a raw material such as a surfactant.

Polymer (I) obtained by this production method
And a polyfunctional compound (II) having two or more functional groups capable of reacting with a hydroxyl group in one molecule as essential components, the composition of the present invention is 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 binders, casting binders, fired brick binders, graft materials, micro) Capsule, glass fiber sizing, etc.), sealing material, urethane foam (hard, semi-hard, soft), urethane RIM, high solid paint, thermosetting elastomer, thermoplastic elastomer, microcellular, artificial leather, synthetic leather, elastic fiber, Textile processing agents, plasticizers, sound absorbing materials, damping materials, artificial marble, ink resins, fibers Lum (laminating adhesives, protective films, etc.), or used in the reactive diluent, etc., also used as various resin additives. In this case, the composition of the present invention not only has flexible and tough mechanical properties, but also has a monomer component (b) constituting the main chain of the polymer (I).
Depending on the type, it has excellent physical properties such as transparency, weather resistance, water resistance, hydrolysis resistance, and chemical resistance, and exhibits very good physical properties.

For example, as the polymer (I), a low molecular weight polymer having a weight average molecular weight of about 1000 to 10000 is used, and this is combined with a bifunctional isocyanate compound or the like to be chain-extended after being applied to a substrate. Compared to the case of using a conventional polymer obtained by copolymerizing a vinyl-based monomer having a functional group when used as an adhesive (usually, a polymer having a weight average molecular weight of 100,000 or more is used) Therefore, 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 pressure-sensitive adhesive composition having an epoch-making effect not found in conventional pressure-sensitive adhesive compositions can be obtained.

When the composition of the present invention is used for an adhesive composition, the composition contains the polymer (I) obtained by the above-mentioned production method as one of the essential components, and therefore, it has a functional group. Compared with the case of using an acrylic polymer obtained by copolymerizing a vinyl-based monomer that has the same adhesive performance, the viscosity of the adhesive composition is low, and therefore the amount of the solvent used. Can be reduced and workability can be improved, and effects that are not available in conventional adhesive compositions can be obtained.
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

The composition of the present invention may be used as an artificial leather composition and / or
Alternatively, when used for synthetic leather composition, the polymer (I)
Is used in combination with a conventionally known isocyanate compound, etc., and therefore, effects that the conventional artificial leather composition and / or synthetic leather composition do not have can be obtained in hydrolysis resistance, heat resistance, and weather resistance. Further, the artificial leather composition and / or the synthetic leather composition using the composition of the present invention has a higher heat resistance than the artificial leather composition and / or the synthetic leather composition using the polyether polyol which is currently used. And is superior in hydrolysis resistance as compared with the artificial leather composition and / or synthetic leather composition using the polyester polyol currently used.

When the composition of the present invention is used for a thermosetting polyurethane elastomer composition, the polymer (I) is used.
Is used in combination with a conventionally known isocyanate compound or the like, and therefore, effects that the conventional thermosetting polyurethane elastomer composition does not have can be obtained in hydrolysis resistance, heat resistance, and light deterioration resistance. In addition, the thermosetting polyurethane elastomer composition using the composition of the present invention is superior in heat resistance to the thermosetting polyurethane elastomer composition using the polyether polyol which is currently used, and is currently used. Hydrolysis resistance is superior to the thermosetting polyurethane elastomer composition using the polyester polyol which is used, and the light deterioration resistance is superior to the thermosetting polyurethane elastomer composition using the polycarbonate polyol currently used. Are better.

When the composition of the present invention is used for a resin composition for flooring, since the polymer (I) is used in combination with a conventionally known isocyanate compound or the like, hydrolysis resistance, heat resistance and light deterioration resistance are obtained. In the above, the effect not obtained by the conventional resin composition for flooring can be obtained. Further, the flooring resin composition using the composition of the present invention is superior in heat resistance to the flooring resin composition using the polyether polyol currently used, and is currently used. Hydrolysis resistance is superior to floor resin compositions using polyester polyols, and light degradation resistance is superior to floor resin compositions currently using polycarbonate polyols.

When the composition of the present invention is used for a printing ink composition, since the polymer (I) is used in combination with a conventionally known isocyanate compound or the like, it has a conventional hydrolysis resistance, heat resistance and weather resistance. The effect not obtained by the printing ink composition can be obtained. In addition, the printing ink composition using the composition of the present invention is superior in heat resistance to the printing ink composition using the polyether polyol currently used, and the polyester polyol currently used is used. Hydrolysis resistance is superior to the conventional printing ink composition.

When the composition of the present invention is used for urethane foam, since the polymer (I) is used in combination with a conventionally known isocyanate compound and the like, flexibility, weather resistance, heat resistance, water resistance and chemical resistance are obtained. In terms of impact resilience, an effect not obtained by conventional urethane foam compositions 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. In the currently marketed acrylic polyol, which has the effect of the main chain being an acrylic ester, since it is a copolymer with hydroxyethyl acrylate, there is a polymer containing three or more hydroxyl groups in one molecule, so artificial leather It is impossible to manufacture thermoplastic polyurethane, which is indispensable for synthetic leather.

When the composition of the present invention is used for a sealing material, by combining the polymer (I) with a conventionally known isocyanate compound or the like, it is flexible and tough.
The effect that the conventional sealing material composition does not have is obtained in weather resistance, heat resistance, water resistance, chemical resistance, and impact resilience. Further, the sealing material using the composition of the present invention,
It is superior in heat resistance to the currently used sealing materials using polyether polyol.

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

The artificial marble obtained from the above-mentioned resin composition for artificial marble has excellent heat resistance and weather resistance, and by using a polymer having a polymerizable unsaturated group at both ends, the present composition is Since the shrinkage due to polymerization is small,
Problems such as cracks occurring during molding are solved.
In addition, since a rubber component is used in the main chain of the polymer, the flexibility of the molded product is greatly improved because the polymer is incorporated into the crosslinked structure at the terminal of the polymer, and a molded product having extremely good impact resistance can be obtained. Can be. Further, for the same reason, there is no chipping at the time of cutting, and the cutting workability is also 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, the addition is added. Since the polymer has a polymerizable unsaturated group at both ends, it is incorporated into the crosslinked structure even after molding, so even if the amount added is increased, problems such as reduced heat resistance do not occur, and flexibility is also high. Is also given enough.

Polyurethane obtained by reacting the polymer (I) with the polyfunctional isocyanate compound (e), and the compound (g) having the polymer (I) having two or more carboxyl groups in one molecule. ), The polyester obtained by reacting with (1) has not only flexible and tough mechanical properties when used as a thermoplastic elastomer or a molding material, but also a vinyl-based monomer that constitutes the main chain of the polymer (I). Ingredient (b)
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.

A polymer having a carboxyl group at both ends has the same transparency as that of the polymer (I) by arbitrarily selecting the kind of the vinyl-based monomer (b) constituting the main chain. Various resins, such as polyester, which have weather resistance, water resistance, hydrolysis resistance, and chemical resistance, and which are derived from a polymer having carboxyl groups at both ends are extremely stretchable (the bending workability is Since it exhibits the characteristics of being good) and toughness, it is a paint, adhesive, thermoplastic elastomer, various molding materials, resin modifiers (impact resistance imparting materials), damping materials, elastic wall materials, floors. Material, fiber processing material, UV
It is useful as a raw material for EB cured resins and the like. Further, the polymer having a carboxyl group at both ends has a feature that it can be used as a curing agent and an additive for an epoxy resin which is difficult to use at the hydroxyl end.

Next, a resin containing as an essential component a polymer having a carboxyl group at both ends and a compound (l) having two or more functional groups capable of reacting with the carboxyl group in one molecule. Like the composition containing the polymer (I), the composition has transparency, weather resistance, and water resistance, by arbitrarily selecting the type of the vinyl-based monomer (b) constituting the main chain. Various resins, such as polyester, which have hydrolysis resistance and chemical resistance, and which are derived from a composition containing a polymer having carboxyl groups at both ends, have very good elongation (bendability is good). In addition, since it exhibits the property of being tough, it has paints, adhesives, thermoplastic elastomers, various molding materials, resin modifiers (impact resistance imparting materials), vibration damping materials, elastic wall materials, floor materials, Textile processing material, UV
It is useful as a raw material for EB cured resins and the like. Further, the composition containing a polymer having carboxyl groups at both ends has a feature that it can be used for an epoxy resin composition which is difficult to use at the hydroxyl end.

In an epoxy resin composition characterized by containing a polymer having a carboxyl group at both ends as an essential component, toughness is improved by adding the polymer having a carboxyl group at both ends to the epoxy resin as a rubber component. In addition to being improved, the heat resistance and the weather resistance have an effect that the conventional epoxy resin composition does not have. That is, the epoxy resin composition using a polymer having carboxyl groups at both ends according to the present invention has higher heat resistance and weather resistance than epoxy resin compositions to which polybutadiene polyol or polybutadiene / acrylonitrile polyol is currently used. Is excellent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08F 20/10 MLY C08F 20/10 MLY 20/26 MML 20/26 MML 30/08 MNU 30/08 MNU C08G 18/62 NEN C08G 18/62 NEN 81/02 NUV 81/02 NUV C08L 57/04 LMK C08L 57/04 LMK 61/20 LNM 61/20 LNM C09J 157/04 JAQ C09J 157/04 JAQ 161/20 JEW 161/20 JEW 175/04 JFC 175/04 JFC C09K 3/10 C09K 3/10 D Z (72) Inventor Hiroyuki Ikeuchi 5-8 Nishimitabicho, Suita City, Osaka Prefecture (72) ) Inventor Fumihide Tamura 5-8 Nishiomitabicho Suita City Osaka Prefecture

Claims (6)

[Claims] 1. A polymer (I) having hydroxyl groups at both ends.
And a compound (II) having two or more functional groups capable of reacting with a hydroxyl group in one molecule, wherein the polymer (I) has the following general formula (1): HO-A- (S) x-B-OH (1) (wherein A and B each represent a divalent organic group, x
Is an integer of 2 to 5. In the method in which the polymerization of the vinyl monomer (b) is carried out using the radical polymerization initiator (c) in the presence of the compound (a) represented by the formula (1), the compound (a) is reacted in the reactor. Always 5 of radical polymerization initiator (c)
It was obtained by carrying out the above-mentioned polymerization, while making it exist in an amount of 0 mol times or more, and substantially not using anything other than the compound (a), the vinyl-based monomer (b) and the radical polymerization initiator (c). What is claimed is: 1. A composition comprising a polymer having hydroxyl groups at both ends. 2. The vinyl monomer (b) comprises a (meth) acrylic acid monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer and a silicon-containing vinyl monomer. The composition according to claim 1, which contains at least one monomer selected from the group as an essential component. 3. The composition according to claim 1, wherein the compound (II) is a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule. 4. The composition according to claim 1, wherein the compound (II) is an aminoplast resin. 5. A pressure-sensitive adhesive using the composition according to claim 3 and / or the composition according to claim 4 as an essential component. 6. A sealing material using the composition according to claim 3 and / or the composition according to claim 4 as an essential component.