JP2594402B2 - Method for producing polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polymer. More specifically, the present invention relates to a method for producing a useful polymer having reactive groups at both terminals, such as a hydroxyl group, a polymerizable unsaturated group, and a carboxyl group, which can react with various functional groups.

[0002]

2. Description of the Related Art Polymers having hydroxyl groups at both ends can be easily converted to other functional groups by reacting the hydroxyl groups at both ends by an appropriate method.
Utilizing the reactivity of the hydroxyl groups at both ends, linearization and / or
Alternatively, the polymer compound is reticulated, resulting in a polymer compound having various favorable physical properties such as strength, heat resistance, weather resistance, and durability.

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 having a functional group introduced into a side chain by copolymerizing a vinyl monomer having a functional group such as a hydroxyl group, a carboxyl group, or an amino group (hereinafter referred to as a copolymer containing a functional group-containing vinyl monomer) When the reaction is carried out using this, the terminal becomes a play portion (free end) which is not incorporated into the resin (crosslinking) structure. In a polymer having hydroxyl groups at both ends, such a terminal is used. Nothing happens.

[0005] Compared to a functional group-containing vinyl monomer copolymer, the dispersion of the distance between the functional groups is extremely small, so that the distance between the reaction points (crosslinking points) is almost constant, and a uniform resin (crosslinking) structure is obtained. 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.

The polymer having a hydroxyl group at both ends is capable of taking advantage of the above-mentioned advantages to provide various resins such as polyester resin, polyurethane resin and polycarbonate resin, paints, adhesives, sealing materials, urethane foams, gel coat materials, Thermoplastic elastomers, molding materials, resin modifiers (impact modifiers), vibration damping materials, elastic wall materials, flooring materials, textile materials, UV / EB cured resins, reactive diluents such as high-solid paints, etc. Very useful as a raw material for Also,
It is also useful as various resin additives and their raw materials.

Paints, adhesives, urethane foams, sealing agents, gel coat materials, thermoplastic elastomers, various molding materials, resin modifiers (impact imparting materials), vibration damping materials,
Examples of the polymer having a hydroxyl group used in applications such as a raw material such as an elastic wall material, a flooring material, a fiber processing material, a UV / EB curing resin, and a reactive diluent such as a high solid paint are vinyl having a hydroxyl group in a side chain. Copolymer of the system monomer, polyether having a hydroxyl group at a terminal, polyester, polybutadiene,
Examples include polycarbonate. 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 and the like having a hydroxyl group at a terminal have a hydroxyl group at a terminal, and thus have few defects such as copolymers of the above-mentioned vinyl monomers having a hydroxyl group in a side chain. Because of the ether bond in the main chain for polyether, the ester bond in the main chain for polyester, and the unsaturated double bond in the main chain for polybutadiene, weather resistance, water resistance, heat resistance, etc. Has the drawback that it is not good.

As described above, at present, paints, adhesives, urethane foams, sealing agents, gel coat materials, thermoplastic elastomers, various molding materials, resin modifiers (impact-resistant materials), vibration dampers A polymer with hydroxyl groups used as a raw material for materials, elastic wall materials, flooring materials, textile materials, UV / EB cured resins, reactive diluents such as high solid paints, etc. Nothing satisfies all the required performances, such as weatherability and water resistance.

It is considered that such a problem can be solved by a vinyl polymer having hydroxyl groups at both ends.
There is currently no established method for industrially producing polymers having hydroxyl groups at both ends from a wide range of vinyl monomers, including polar vinyl monomers such as methacrylic acid and methacrylic acid esters. It is.

As a method for producing a vinyl polymer having a hydroxyl group at a terminal, for example, 2-mercaptoethanol or the like is used as a chain transfer agent to introduce one hydroxyl group to one terminal of the polymer and to prepare 2-hydroxy methacrylate. There is a method of obtaining a polymer having a terminal hydroxyl group 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 are introduced per one molecule of the polymer, only one of the average two hydroxyl groups is introduced into one end of the polymer. 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 the polymer having a hydroxyl group at both terminals as described above. 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.

As a method for producing a vinyl polymer having a hydroxyl group at both ends, for example, as shown in the following (i) to (iii), a vinyl polymer is used in the presence of various initiators and chain transfer agents. There is a method of radically polymerizing a monomer. (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) A method of performing thermal polymerization or photopolymerization using dithiocarbamate or thiuram disulfide having a hydroxyl group as an initiator, or 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 polymerization using an initiator (see JP-A-61-271306).

(Iii) A method of obtaining a polymer having hydroxyl groups at both ends by polymerization using disulfide, trisulfide or the like having a hydroxyl group at both ends as a chain transfer agent (see JP-A-54-47782).

[0016]

However, the above-mentioned conventional methods for producing a polymer having hydroxyl groups at both ends (i) to (i).
(Iii) has drawbacks as follows, and a polymer having hydroxyl groups at both ends is reliably, inexpensively, easily, and industrially synthesized from many types of vinyl monomers. Not easy.

First, in the method (i), usable vinyl monomers are limited to butadiene and styrene, and polar vinyl monomers such as acrylates and methacrylates 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 method (iii), no consideration is given to the ratio of the chain transfer agent to the initiator. There was a problem that a polymer fragment having a hydroxyl group only at one end was formed as a by-product, and a polymer having a small number of terminal hydroxyl groups was formed. 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.
For this reason, a polymer having hydroxyl groups at both ends is used as an intermediate, and a polymer having a polymerizable unsaturated group or a carboxyl group at both ends, which is produced by further reacting this intermediate, is also used. However, an industrial production method has not been established yet.

In view of such circumstances, the present invention has been developed from a wide variety of vinyl monomers including polar vinyl monomers such as acrylic acid, acrylic acid ester, methacrylic acid and methacrylic acid ester to both ends. A polymer having a hydroxyl group, a polymerizable unsaturated group, and a carboxyl group as a reactive group,
It is an object to provide a method that can be obtained easily, inexpensively, and efficiently.

[0020]

In order to solve the above-mentioned problems, a method for producing a polymer having a hydroxyl group at both terminals according to the present invention is represented by the following general formula (1): HO-A- (S) x- B-OH (1) (wherein, A and B each represent a divalent organic group, and 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)
The polymerization is carried out in an amount of at least 0 mole times and using substantially no compound other than the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c). .

The method for producing a polymer having polymerizable unsaturated groups at both ends according to the present invention is represented by the following general formula (1): HO-A- (S) x-B-OH (1) Wherein A and B each represent a divalent organic group, and 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 is present in an amount of 0 mole times or more, and substantially free of any compound other than the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c). Reacting the polymer (I) having a hydroxyl group with a compound (h) having two types of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group in one molecule. I do.

The method for producing a polymer having carboxyl groups at both ends according to the present invention is represented by the following general formula (1): HO-A- (S) x-B-OH (1) And B each represent a divalent organic group, and 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 is present in an amount of 0 mol times or more, and substantially free of any compound other than the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c). Reacting the polymer (I) having a hydroxyl group with a compound (j) and / or an acid anhydride having two reactive groups of a functional group capable of reacting with a hydroxyl group and a carboxyl group in one molecule. Features.

Hereinafter, first, a polymer having a hydroxyl group at both ends (hereinafter, a “polymer having a hydroxyl group at both ends” may be referred to as a “polymer (I)”) according to the present invention. The method will be described. The general formula (1)
Specific examples of the compound (a) represented by are not particularly limited, and include, 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-hydroxy Ethyl) pentasulfide, bis (3-hydroxypropyl) disulfide, bis (3-hydroxypropyl) trisulfide, bis (3-hydroxypropyl) tetrasulfide, bis (2-hydroxypropyl) disulfide, bis (2-hydroxypropyl) Trisulfide, bis (2-hydroxypropyl) tetrasulfide, bis (4-hydroxybutyl) disulfide, bis (4-hydroxybutyl) trisulfide, bis (4-hydroxybutyl) tetrasulfide , Bis (8-hydroxy-octyl) disulfide, bis (8-hydroxy-octyl) trisulfide, bis (8-hydroxy-octyl)
Hydroxyalkyl di, such as tetrasulfide, tri,
Tetra or pentasulfides 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'-tetrathiodioctanoic acid, 2,2'-dithiodibenzoic acid, 2,2'-trithiodibenzoic acid, 2,2'-tetrathiodibenzoic acid, 2,2'-dithiodinicotinic acid,
Di (2-hydroxyethyl) ester (ethylene oxide adduct) or di (hydroxypropyl) of di, tri or tetrasulfide dicarboxylic acids such as 2,2'-trithiodinicotinic acid and 2,2'-tetrathiodinicotinic acid ) Esters (propylene oxide adducts) and the like, and these can be used alone or in combination of two or more.

The vinyl monomer (b) used in the present invention is not particularly limited as long as it is a conventionally known vinyl monomer. For example, (meth) acrylic acid;
Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, Alkyl (meth) acrylates such as stearyl (meth) acrylate; aryl (meth) acrylates such as benzyl (meth) acrylate;
2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ-
(Meth) acrylic acid substituent-containing alkyl esters such as (methacryloyloxypropyl) trimethoxysilane; (meth) acrylic acid derivatives such as methoxyethyl (meth) acrylate and ethylene oxide adduct of (meth) acrylic acid; Trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2 (meth) acrylate
-Perfluorobutylethyl, (meth) acrylic acid 2-
(Meth) acrylic acid monomers such as perfluoroalkyl esters such as perfluoroethyl; and styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and sodium salts thereof. Aromatic vinyl monomers; perfluoromethyl (meth) acrylate, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2- (perfluoroethylethyl) (meth) acrylate, 2-perfluoromethyl-2- (meth) acrylate, trifluoromethyl (meth) acrylate, 2-perfluoro (meth) acrylate Ethyl-2-perfluorobutylethyl, (meth) ac Fluorine-containing vinyl such as 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, perfluoroethylene, perfluoropropylene, and vinylidene fluoride Silicon-containing vinyl monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, and γ- (methacryloyloxypropyl) trimethoxysilane; maleic anhydride, maleic acid, and monoalkyl esters of maleic acid; Dialkyl esters; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmale Maleimide derivatives such as amide, phenylmaleimide and cyclohexylmaleimide; vinyl monomers containing a nitrile group such as acrylonitrile and methacrylonitrile; vinyl monomers containing an amide group such as acrylamide and methacrylamide; vinyl acetate and propionic acid Vinyl esters such as vinyl, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride and allyl alcohol. These may be used alone or in combination of two or more.

As described above, the vinyl monomer (b) used in the present invention may have a functional group such as a hydroxyl group, a carboxyl group, or an amino group in the molecule. 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 monomer having a functional group is not particularly limited. For example, in the case of the vinyl monomer having a hydroxyl group, the amount is
The amount of the vinyl monomer having a hydroxyl group 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 amount of the vinyl monomer having a carboxyl group is 0.5 to 0.5% based on the total amount of the vinyl monomer (b) used.
The content is preferably 25% by weight, more preferably 1 to 10% by weight.

The vinyl monomer (b) is, 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 to inorganic materials 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) used in the present invention is not particularly limited, but includes, for example, isobutyryl peroxide, cumyl peroxy neodecanoate, diisopropyloxy dicarbonate,
Di (n-propyl) peroxydicarbonate, di (2
-Ethoxyethyl) peroxydicarbonate, di (2
-Ethylhexyl) peroxy dicarbonate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 3,3,5-
Trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumylperoxyoctate, succinic peroxide, acetyl peroxide, t-butylperoxy (2-ethylhexanate), m-toluoyl peroxide, benzoyl Peroxide, t-butyl peroxyisobutyrate, 1,
1'-bis (t-butylperoxy) cyclohexane,
t-butylperoxymaleic acid, t-butylperoxylaurate, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxyhexane,
t-butyl peroxyacetate, 2,2'-bis (t
-Butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4'-bis (t-butylperoxy) valerate, di- (t-butylperoxy) isophthalate, methyl ethyl ketone peroxide, Mil peroxide, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexane, 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-
Organic peroxides such as 3,1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide; hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate Inorganic peroxides such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile),
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)
Redox initiators such as hydrogen peroxide-Fe (II) salt, persulfate-sodium bisulfite, cumene hydroperoxide-Fe (II) salt, benzoyl peroxide-dimethylaniline; And photosensitizers such as dibenzyl and acetophenone. Among them, only one kind may be used, or two or more kinds may be used in combination.

However, many initiators having various functional groups, for example, hydroxyl group, amino group and carboxyl group, have high hydrophilicity, and many of them are soluble in lipophilic vinyl monomers. There are many things that 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 production method of the present invention, during the reaction, the molar ratio ((a) / (c)) of the compound (a) and the radical polymerization initiator (c) in the reactor must always be 50 or more. Must be 60 or more, and most preferably 100 or more. In the manufacturing method of the present invention,
In the polymerization process, components other than the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c)
Substantially not used. Specifically, the components other than the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c) are adjusted to be about 10% by weight or less of the whole. The components other than (a), (b) and (c) are preferably 5% by weight or less, and most preferably not used at all.

In the polymerization process of the production method of the present invention, during the polymerization, the molar ratio ((a) / (c)) of the compound (a) and the radical polymerization initiator (c) in the reactor is always constant. 5
Any polymerization method may be used as long as it is 0 or more. For example, compound (a), vinyl monomer (b)
The radical polymerization initiator (c) and the radical polymerization initiator (c) may be charged at once from the beginning to carry out the polymerization, or the polymerization may be carried out while supplying each component to the polymerization system as needed. 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,
Since the radical polymerization initiator (c) is preferably supplied as a solution of the vinyl monomer (b), the initiator (c) is an initiator that is sufficiently dissolved in the vinyl monomer (b). Preferably, it is used. 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 production method of the present invention, the ratio of the compound (a) to the vinyl monomer (b) used is not particularly limited, but the radical generated from the initiator (c) is converted into the 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 directly adding to the vinyl monomer (b) to initiate polymerization without causing chain transfer to vinyl, It is preferable that the amount of the compound (a) is larger than that of the system monomer (b). More specifically, the weight ratio of the compound (a) to the vinyl monomer (b) (compound (a) / vinyl monomer (b)) is preferably 0.5 or more.
More preferably, it is 0 or more.

The polymerization vessel used in the present invention may be of a batch type such as a flask type or a kneader, a tube type of a piston flow, a twin screw extruder or a continuous type depending on the viscosity of the polymer. A continuous type such as a kneader may be used. A semi-batch type reactor can be used 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 the residence time must be constant. From the viewpoint of good productivity and the like, it is preferable to use a tubular reactor, an extruder, a continuous kneader, or the like.
Regarding the use of the tubular reactor, extruder and continuous kneader, those with low viscosity after polymerization use the tubular reactor,
It is preferable to use an extruder or a continuous kneader for those having 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 (manufactured by Noritake Company or Sumitomo Sulzer). Any tube reactor can be used, but from the viewpoint of mixing and heat exchange efficiency, it is preferable to use a tube reactor using a mixer having no movable part. 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.

There is no particular limitation on the polymerization temperature in the production method of the present invention, and there is no problem as long as it is about from room temperature to 200 ° C. in which ordinary radical polymerization is performed. In the present invention, the reaction can be carried out under pressure in an autoclave or an extruder. Although the average molecular weight of the polymer (I) obtained by the production method of the present invention is not particularly limited, the number average molecular weight is preferably at least one in order to exhibit the characteristics resulting from having reactive hydroxyl groups at both terminals. , 500 to 100,000, more preferably 1,000 to 10,000.

The average number of terminal hydroxyl groups (Fn (OH)) of the polymer (I) obtained by the production method of the present invention is ideally 2.0, but may be 1.8 to 2.0. If this is the case, physical properties equivalent to almost ideal ones can be exhibited, which is very preferable. 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 (Fn (OH)) of the polymer (I) to be obtained in the present invention may be 1.5 or more.

The polymer (I) obtained by the production method of the present invention can easily convert the hydroxyl groups at both ends thereof into a polymerizable unsaturated group such as a vinyl group or an amino group by utilizing a conventionally known organic reaction or the like. Can be converted to useful terminal functional groups such as carboxyl group, ethynyl group, epoxy group, silanol group, alkoxysilyl group, hydrosilyl group, mercapto group, oxazoline group, maleimide group, azlactone group, lactone group, bromine and chlorine. it can.

Next, the composition containing the polymer (I) obtained by the production method of the present invention, that is, the composition containing the polymer (I) will be described. As described above, the polymer (I) -containing composition comprises a polymer (I) obtained by the production method of the present invention and a compound (d) having two or more functional groups capable of reacting with a hydroxyl group in one molecule. ) As essential components. As the polymer (I), one type may be used alone, or two or more types may be used in combination. The weight ratio of the polymer (I) and the compound (d) (polymer (I) / compound (d)) contained in the composition is not particularly limited, but is 99.99 / 0.01. ４０40/60, more preferably 99.9 / 0.1-60 / 40.

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

The number of functional groups capable of reacting with a hydroxyl group is 2 per molecule.
The compound (d) having at least two isomers is not particularly limited, and examples thereof include a compound (e) having two or more isocyanate groups in one molecule, and amino such as methylolated melamine and its alkyl etherified product or low condensed product. Compounds (g) having two or more carboxyl groups in one molecule such as plast resin (f), polyfunctional carboxylic acids and their halides are exemplified.

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 make better use of the weather resistance of the composition comprising the polymer (I) and the polyfunctional isocyanate compound (e), the polyfunctional isocyanate compound (e)
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 mixing ratio of the polymer (I) and 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 polymer (I) -containing composition, and the polyfunctional isocyanate compound (e), if necessary, an organic compound may be used. Known catalysts such as tin compounds and tertiary amines can be used freely. The aminoplast resin (f) used in the polymer (I) -containing composition is not particularly limited. For example, a reaction product of a triazine ring-containing compound represented by the following general formula 1 with formaldehyde (a methylol compound) ), Low-condensation products of the triazine ring-containing compound and formaldehyde, derivatives thereof, and urea resins.

[0045]

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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. 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 hexamethoxymethyl melamine and tetramethoxymethyl benzoguanamine. 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.

The aminoplast resin (f) exemplified 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 polymer (I) -containing composition containing the polymer (I) and the aminoplast resin (f) as the compound (d) as essential components (Weight ratio) is preferably 95: 5 to 50:50, and more preferably 80:20 to 60:40.

In a composition containing the polymer (I) and the aminoplast resin (f) as essential components, a composition known in the art such as paratoluenesulfonic acid, benzenesulfonic acid or the like for promoting the reaction is used. It is free to use this catalyst. Compound (g) having two or more carboxyl groups in one molecule, which is used in the polymer (I) -containing composition
As is not particularly limited, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, phthalic anhydride, terephthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, Pyromellitic anhydride, maleic acid, maleic anhydride, fumaric acid,
Examples thereof include polyfunctional carboxylic acids such as itaconic acid, diphenic acid, and naphthalenedicarboxylic acid, and anhydrides thereof, and halides thereof and 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. Compound (g)
And the molar ratio of hydroxyl groups in the polymer (I) (compound (g)
/ Hydroxyl group in the polymer (I)) is preferably 1 to 3, and more preferably 1 to 2.

When the polymer (I) -containing composition is used as a coating composition, a certain degree of crosslinking density is required because the hardness of the coating film is required. Therefore, as the polymer (I) used for paint applications, the hydroxyl value is 20 to 2
About 00 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 coating applications is preferably from -30C to 100C, and from -10C to 60C.
Is more preferred. 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 (d), it is preferable to copolymerize an acid group-containing vinyl monomer as an internal acid catalyst.
When the polymer (I) -containing composition 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, Ether polyol, polyester polyol, polycarbonate polyol,
Polybutadiene polyol, polyolefin polyol, etc.), and conventionally known coating resins.

When the composition containing the polymer (I) is used as a composition for an adhesive, the Tg of the polymer (I) is preferably -20 ° C. or lower, and the molecular weight (weight average molecular weight) is , 1000 to 1,000,000. Further, in order to further improve the adhesiveness with the substrate, it is preferable to copolymerize an acid group-containing monomer. When the polymer (I) -containing composition is used as a composition for a pressure-sensitive adhesive, the composition may contain, if necessary, a conventionally known resin for a pressure-sensitive adhesive, a tackifier, a plasticizer, a filler, Additives such as anti-aging agents may be included. The tackifier that can be used is not particularly limited, for example,
Rosin type, rosin ester type, polyterpene resin, chroman-indene resin, petroleum resin, terpene phenol resin and the like can be mentioned. 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, for example,
Examples include rubber-based antioxidants (phenol-based, amine-based) and metal dithiocarbamates. Each of the tackifiers, plasticizers, fillers and antioxidants listed above may be used alone or in combination of two or more.

When the composition containing the polymer (I) is used as a composition for an adhesive, the molecular weight (weight average molecular weight) of the polymer (I) is preferably 1,000 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 polymer (I) -containing composition is used as a composition for an adhesive, the composition may contain, if necessary, conventionally known polyols (low-molecular-weight polyols and high-molecular-weight polyols), Additives such as imparting agents, coupling agents, thixotropic agents, inorganic fillers and stabilizers may be included. The polyols that can be used are not particularly limited. For example, low molecular weight polyols such as ethylene glycol (also referred to as EG), diethylene glycol (also referred to as DEG), dipropylene glycol (also referred to as DPG),
1,4-butanediol (also called 1,4-BD),
1,6-hexanediol (also referred to as 1,6-HD),
Neopentyl glycol (also referred to as NPG), trimethylolpropane (also referred to as TMP), and the like. Polyether polyol [polyethylene glycol (also referred to as PEG), polypropylene glycol (also referred to as PPG), ethylene oxide
Propylene oxide copolymer (also called EO / PO copolymer), polytetramethylene glycol (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, for example,
Examples 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, for example,
Examples include ultraviolet absorbers, antioxidants, heat stabilizers, and hydrolysis stabilizers. 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 use of the above-mentioned adhesive is not particularly limited, but for example, an adhesive for food packaging, an adhesive for shoes and footwear, an adhesive for cosmetic paper, an adhesive for wood, an adhesive for structures (automobiles,
Septic tanks, housing) adhesives, magnetic tape binders, fiber processing binders, fiber treatment agents and the like. When the composition containing the polymer (I) is used as a composition for artificial leather and / or synthetic leather, the composition may contain, if necessary, conventionally known compounds used for artificial leather and synthetic leather. Can be used. For example, chain extenders,
High molecular weight polyols, organic isocyanates, solvents and the like. The chain extender is not particularly limited. For example, examples of polyol-based chain extenders include EG, DEG,
Triethylene glycol (also called TEG), DPG,
1,4-BD, 1,6-HD, NPG, hydrogenated bisphenol A, and the like. Examples of the polyamine-based chain extender include 4,4′-diaminodiphenylmethane, tolylenediamine, and 4,4 ′. -Diaminodicyclohexylmethane, piperazine and the like. One of these may be used alone, or two or more thereof may be used in combination. Examples of high molecular weight polyols include polyether polyols (PEG, PPG, EO / PO copolymer, PTME
G), one or more of polyester polyol, castor oil, liquid polybutadiene, polycarbonate diol, acrylic polyol and the like are used. As the organic isocyanate, one or more kinds of 4,4′-diphenylmethane diisocyanate (also referred to as MDI), toluylene diisocyanate (also referred to as TDI), isophorone diisocyanate, hexamethylene diisocyanate, and the like are used. As the solvent, dimethylformamide (also referred to as DMF), methyl ethyl ketone (M
EK), 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. One or more of these are 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 containing the polymer (I) is used as a printing ink composition, all of the conventionally known compounds used for printing ink 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 extender is not particularly limited. For example, examples of the polyol-based chain extender include EG, DEG, TEG, DP
Aliphatic glycols such as G, 1,4-BD, 1,6-HD, neopentyl glycol, alicyclic glycols such as 1,4-cyclohexane glycol, xylylene glycol, 1,4-dihydroxyethylbenzene, water Aromatic glycols such as added bisphenol A and the like, and polyamine-based chain extenders such as ethylene diamine, aliphatic diamines such as propylene diamine
Monoethanolamine, alkanolamines such as diethanolamine, 4,4′-diaminodiphenylmethane, tolylenediamine, 4,4′-diaminodicyclohexylmethane, piperazine, and the like.
One type may be used alone, or two or more types may be used in combination. Examples of high molecular weight polyols include polyether polyols (PEG, PPG, EO / PO copolymer, PTME
G), polyester polyol, liquid polybutadiene,
One or more kinds of polycarbonate diols and the like can 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 perchrene; One kind of ethers such as dioxane, esters such as cellosolve acetate, ethyl acetate and butyl acetate may be used alone,
Two or more kinds may be used in combination. If necessary, an isocyanate compound having three or more functionalities can be used as a crosslinking agent. In addition, if necessary, a urethanization catalyst,
Accelerators, colorants such as pigments, surfactants, ultraviolet absorbers,
Antioxidants, hydrolysis inhibitors and the like can be used. Also,
In the production of the printing ink composition, if necessary, a polymer such as nitrocellulose, polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, polyamide, or an acrylate polymer may be mixed.

When the composition containing the polymer (I) is used as a thermosetting polyurethane elastomer composition, the composition may contain, if necessary, a conventionally known compound used in a usual thermosetting polyurethane elastomer composition. Can all be used. For example, chain extenders, curing agents,
High molecular weight polyols, organic isocyanates and the like. The chain extender is not particularly limited. For example, as the polyol-based chain 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-cyclohexane glycol; Xylylene glycol, 1,4-dihydroxyethylbenzene, aromatic glycols such as hydrogenated bisphenol A, and the like,
These may be used alone or in combination of two or more. As a 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, a conventionally known one-shot method, prepolymer method, or 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 containing the polymer (I) is used as a resin composition for flooring materials, if necessary, all of the conventionally known compounds used in resin compositions for flooring materials may be included in the composition. Can be used. For example, curing agents, high molecular weight polyols, organic isocyanates, and the like. The curing agent is not particularly limited. Examples of the polyol curing agent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, Aliphatic glycols such as 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, glycerin and trimethylolpropane;
Alicyclic glycols such as 1,4-cyclohexane glycol, xylylene glycol, 1,4-dihydroxyethylbenzene, aromatic glycols such as hydrogenated bisphenol A, and the like, and amine-based curing agents 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 N
aCl complex, 4,4'-methylenebis-o-chloroaniline, 1,2-bis (2-aminophenylthio) ethane, trimethylene glycol di-p-aminobenzoate, di (methylthio) tolylenediamine, ethylenediamine, triamine Ethylenetetramine, hexamethylenediaminecarbamate and the like can be mentioned, and these may be used alone or in combination of two or more. As high molecular weight polyols, polyether polyols (PE
G, PPG, EO / PO copolymer, PTMEG), polyester polyol, polymer polyol, liquid polybutadiene, polyolefin polyol, polycarbonate diol, castor oil and the like. 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, and diphenyldimethyl. Methane-4,4'-diisocyanate, toluylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3- or 1,4-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, bis (isocyanatomethyl) cycloxane , Triphenylmethane triisocyanate or the like. 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 urethanizing catalyst, an accelerator, a plasticizer, a tackifier, a coloring agent such as a pigment,
Surfactants, UV absorbers, antioxidants, hydrolysis inhibitors, fillers, defoamers and the like can be used.

The use of the resin composition for flooring is not particularly limited, and examples thereof include flooring for ships and buildings, coating film waterproofing agents, sheet waterproofing agents, spraying waterproofing agents, sealing materials, artificial turf and the like. Adhesives, asphalt modifiers for road pavement, elastic pavement materials for tennis courts and athletic fields, concrete floor covering concrete protection materials, and the like. When the polymer (I) -containing composition is used as a urethane foam composition, the molecular weight (weight average molecular weight) of the polymer (I) is from 1,000 to 1,000.
Preferably it is 1,000,000.

When the composition containing the polymer (I) is used as a urethane foam composition, the composition may contain, if necessary, conventionally known polyols (polymers obtained by the production method of the present invention). Other than I), low-molecular-weight polyols, high-molecular-weight polyols, etc.), polyisocyanates (eg, TDI, MDI, etc.), catalysts (eg, amine-based, tin-based, etc.), water, surfactants (eg, silicon-based) , Nonionic, ionic, etc.), additives (eg, flame retardants, antimicrobial agents, coloring agents, fillers, stabilizers, etc.), foaming aids (eg, halogenated hydrocarbons, etc.), etc. You may.

When the composition containing the polymer (I) is used as a sealing material composition, the molecular weight (weight average molecular weight) of the polymer (I) is preferably 1,000 to 1,000,000. When the polymer (I) -containing composition is used as a sealing material composition, the composition may contain, if necessary, conventionally known polyols (other than the polymer (I) obtained by the production method of the present invention). High molecular weight polyols, etc.), polyisocyanates (eg, TDI, MDI
Etc.), catalysts (e.g., amine-based, tin-based, lead-based, etc.), inorganic fillers (e.g., calcium carbonate, talc, clay, silica, carbon black, titanium white, etc.), plasticizers [e.g., dioctyl phthalate (e.g., DOP), di-i-decyl phthalate (also referred to as DIDP), dioctyl adipate (also referred to as DOA), etc., anti-sagging agents (eg, colloidal silica, hydrogenated castor oil, organic bentonite, surface-treated calcium carbonate) Antioxidants (eg, hindered phenols, benzotriazole,
Hindered amines, etc.), foam inhibitors (eg, dehydrating agents, carbon dioxide absorbents, etc.), and the like.

When a polymer obtained by converting a hydroxyl group of the polymer (I) obtained by the production method of the present invention into a hydroxysilyl group, an alkoxysilyl group or a mercapto group is used as an essential component of the sealing material composition, The sealant composition results in a sealant composition having a different crosslinking system than urethane. Next, according to the present invention, a polymer having a polymerizable unsaturated group at both ends (hereinafter, referred to as a polymer)
The “polymer having a polymerizable unsaturated group at both terminals” may be referred to as “polymer (II-1)”. ) Will be described.

The process for producing the polymer (II-1) according to the present invention is characterized in that the polymer (I) obtained by the process described in detail above comprises a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group. And a compound (h) having two types of reactive groups in one molecule. The compound (h) having two types of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group, in one molecule is not particularly limited, and examples thereof include an isocyanate group, a carboxyl group, Examples include a vinyl monomer having a methylolated triazine ring and the like. More specifically,
For example, methacryloyloxyethyl isocyanate,
Examples include methacryloyl isocyanate, isopropenyl dimethylbenzyl isocyanate, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and halides of carboxyl groups thereof, and methylolated vinyl guanamine.

In this reaction, a solvent or a conventionally known catalyst can be used freely. 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 (II-1) obtained by this production method is used as an essential component of a resin composition, other components contained in the resin composition include, for example, a polymerizable polymer in one molecule. A vinyl monomer having one saturated group is exemplified. 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 may be, for example, light, EB, UV, radiation,
Heat or the like can be used.

The polymer (II-1) obtained by this production method
Examples of the resin composition containing a vinyl monomer having one polymerizable unsaturated group in one molecule as an essential component include:
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 (II-1) to the vinyl monomer (polymer (II-1) / vinyl monomer) contained in the gel coat resin composition is not particularly limited. Not preferred, but preferably 10 / 90-60 / 40, 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. In addition, the ratio is 60/40
If the size is larger, 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,
It is preferable that the Tg of the polymer (II-1) and the Tg of the vinyl monomer used in this application are both 20 ° C. or higher. When it is necessary to increase the crosslink density in order to obtain surface hardness, a vinyl monomer having a hydroxyl group may be copolymerized in the polymer (II-1), or a polyfunctional vinyl monomer may be used. 50% by weight of (i) based on the total amount of the polymer (II-1), a vinyl monomer having one polymerizable unsaturated group in one molecule and a polyfunctional vinyl monomer (i). % Or less.

If necessary, a polymerization inhibitor such as hydroquinone, catechol, 2,6-ditert-butylparacresol is added to the gel coat resin composition. It is cured by 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.

The gel coat resin composition may further contain, if necessary, a dye, a plasticizer, an ultraviolet absorber, and other known thixotropic agents such as silica, asbestos powder, hydrogenated castor oil, and fatty acid amide. And various additives such as a filler, a stabilizer, an antifoaming agent, and a leveling agent. 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 monomer (i) to be added as necessary to the resin composition for artificial marble is not particularly limited, but ethylene glycol di (meth) acrylate, propylene glycol di (meth) Multifunctional (meth) 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 include acrylates, methylenebis (meth) acrylamide, divinylbenzene, and the like. The addition amount of the polyfunctional vinyl monomer (i) is not particularly limited, but may be a polymer (II-1), a vinyl monomer having one polymerizable unsaturated group in one molecule, and a polyfunctional vinyl. It is preferably 40% by weight or less based on the total amount of the system 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.

The fillers that are optionally added to the artificial marble resin composition include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium carbonate, talc, clay, silica, quartz, alumina, zirconia,
Glass powder, glass fiber, marble, limestone, pyroxene,
Examples include natural crushed stones such as amphibole, sandstone, granite and basalt, and crushed products of synthetic resins such as unsaturated polyester resins, thermosetting acrylic resins and melamine resins. The addition amount of the filler is not particularly limited, but the polymer (II-
1) It is preferably 100 to 800% by weight based on the total amount of the vinyl monomer having one polymerizable unsaturated group in one molecule and the polyfunctional vinyl monomer (i). This addition amount is 1
If the amount is less than 00% by weight, heat resistance and flame retardancy may be insufficient. If the amount is more than 800% by weight, polymer (II-1) may contain a polymerizable unsaturated group in one molecule. Dispersibility of the filler in the vinyl monomer and the polyfunctional vinyl monomer (i) having one is insufficient, or the fluidity at the time of molding and curing is impaired, so that a uniform artificial marble can be obtained. Or not.

The hardener added to the artificial marble resin composition as required is not particularly limited. For example, benzoyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, bis (4-t-butylcyclohexyl) ) Peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxyoctoate and the like. 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 to be added to the resin composition for artificial marble as required is not particularly limited. Examples thereof include (meth) acrylic polymers such as polymethyl methacrylate, 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, it is preferable to use a small amount of the thermoplastic polymer for reducing the shrinkage as much as possible, and there is no particular limitation. It is preferably used in an amount of 100% by weight or less based on the total amount of the monomer and the polyfunctional vinyl monomer (i).

Next, a polymer having a carboxyl group at both ends according to the present invention (hereinafter, a “polymer having a carboxyl group at both ends” is sometimes referred to as a “polymer (II-2)”). A method of manufacturing the device will be described. The production method of the polymer (II-2) according to the present invention is characterized in that the polymer (I) obtained by the production method described in detail above has two reactive groups of a functional group capable of reacting with a hydroxyl group and a carboxyl group. It is characterized by reacting a compound (j) having a group in one molecule and / or an acid anhydride.

The compound (j) having two reactive groups, a functional group capable of reacting with a hydroxyl group and a carboxyl group, in one molecule is not particularly limited. Examples thereof include oxalic acid, malonic acid and succinic acid. Acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid,
Dodecanedioic acid, phthalic acid, terephthalic acid, maleic acid,
Examples include dibasic acids such as 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, a solvent or a conventionally known catalyst may be used freely. 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 a hydroxyl group of the compound (j) is a carboxyl group (for example, when the compound (j) is a dibasic acid) is not particularly limited. -100 ° C is preferred. 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, the polymer (II
-2) and a compound (k) having two or more functional groups capable of reacting with a carboxyl group in one molecule will be described. As the polymer (II-2), only one type may be used, or two or more types may be used in combination. Further, the weight ratio of the polymer (II-2) to the compound (k) contained in the resin composition (polymer (II-2)
/ Compound (k)) is not particularly limited, but is 99.9.
9 / 0.01 to 40/60, preferably 9 / 0.01 to 40/60.
More preferably, it is 9.9 / 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. For example, a compound (k) having two or more epoxy groups in one molecule, A compound having two or more hydroxyl groups in a molecule, a compound having two or more amino groups in a molecule, a compound having two or more mercapto groups in a 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 (II-2) may be used as an essential component of an 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. For example, bisphenol A, bisphenol F, phenol novolak, cresol novolak, Glycidyl ethers of phenols such as brominated bisphenol A; glycidyl ethers of alcohols such as butanol, butanediol, polyethylene glycol and 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.

The epoxy resin composition may be freely added with additives such as a filler, a pigment and a curing agent, if necessary. 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, a polyol component (l) containing the polymer (I) as an essential component, and a polyfunctional isocyanate compound (e) having two or more isocyanate groups in one molecule.
Will be described below. 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).
Diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,3-
Low molecular weight polyols such as butanediol, 1,6-hexanediol, trimethylolpropane, and pentaerythritol; polyether polyols such as polyethylene glycol, polypropylene glycol, and polypropylene glycol-polyethylene glycol block copolymer; Polyester polyol, polycarbonate polyol, butadiene and butadiene / acrylonitrile synthesized from polyfunctional carboxylic acids such as acid, phthalic anhydride, terephthalic acid, maleic acid, maleic anhydride, fumaric acid, malonic acid, succinic acid, glutaric acid and adipic acid Selected from diene-based polyols consisting of copolymer main chains, polyolefin polyols, polymer polyols, polymer polyols such as acrylic polyols, etc. One or more polyols has can be used in combination.

In the 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. ) Is reacted with the polyfunctional isocyanate compound (e) to synthesize a polymer (oligomer) having isocyanate groups at both ends, and then, in the next step, the polymer (oligomer) is A multi-stage reaction for synthesizing a polyurethane by further reacting with another (or the same) polyol component and repeating this may be used. 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 it is desired to use a variety of polyols as the polyol component (l) and synthesize a polyurethane having a block structure in which the sequence of ABA, (AB) _n , ABCBA, etc. is controlled, the above-mentioned multi-stage reaction is preferably used. . 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 a 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 a result, a polymer having a hydroxyl group in addition to both ends is used as the polymer (I), 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 amounts of the polymer (I) and 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, there is no problem if the molar ratio (NCO / OH) of the isocyanate group in the compound (e) to the hydroxyl group in the polymer having hydroxyl groups at both ends is higher than 1. In order to prevent a molecular weight increase at this stage and synthesize a polyurethane having a clear block structure,
1.2 to 2.0 is preferable, and 1.5 to 2.0 is more preferable. Further, the isocyanate group in the polyfunctional isocyanate compound (e) in the case of the one-step reaction and the polymer (I)
The molar ratio (NCO / OH) to the hydroxyl group in the solution is 0.5 to
It is preferably 1.5, and more preferably 0.8 to 1.2.

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

The polyol component (1) containing the polymer (I) as an essential component and used in synthesizing the 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 it is desired to use a variety of polyols as the polyol component (l) and synthesize a polyester having a block structure with sequence control such as ABA, (AB) _n , and ABCBA, it is preferable to use the above-described multi-stage 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 sufficiently exhibit the performance as a thermoplastic elastomer, a block structure in which hard segments and soft segments are regularly arranged is necessary. Therefore, it is preferable to synthesize by a multi-step reaction as described above. . 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 include, if necessary, other components such as fillers such as glass fiber and pulp contained in conventional molding materials. A release material, a pigment such as calcium carbonate and titanium oxide, an ultraviolet absorber, an antioxidant, 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, a block polymer characterized by containing the polymer (I) obtained by the production method of the present invention as an essential component will be described. The method for obtaining the block polymer is not particularly limited, and examples thereof include the following four methods. Two or more polyols are used as the polyol component (l) containing the polymer (I) obtained by the production method of the present invention as an essential component, and two or more functional groups capable of reacting with a hydroxyl group in one molecule are used. A method of reacting the compound having the above.

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

Using the polymer (I) obtained by the production method of the present invention as an initiator, ethylene oxide,
A method of obtaining an ABA block polymer by ring-opening polymerization of one or more cyclic ethers such as propylene oxide and tetrahydrofuran. Said,
In the methods and, the functional group capable of reacting with the hydroxyl group is not particularly limited, for example, isocyanate group, carboxyl group, triazine ring, methylolated triazine ring, acid anhydride, azlactone ring, silanol group, carbonate group, Examples include an epoxy group and an acid halide group.

The method of the reaction in the above methods is not particularly limited. For example, any of the one-stage reaction method and the multi-stage reaction method described in the above description of the polyurethane and polyester may be 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.

Although the structure of the block polymer is not particularly limited, it is 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.

[0098]

According to the process for producing the polymer (I) of the present invention, the molar ratio ((a) / (c)) of the compound (a) and the radical polymerization initiator (c) in the polymerization vessel during the polymerization is calculated as follows: By always maintaining the value at 50 or more, the by-product of a polymer having no hydroxyl group at one or both terminals is suppressed. That is, when the molar ratio between the compound (a) and the radical polymerization initiator (c) in the polymerization vessel during the polymerization becomes less than 50, the radical generated from the radical polymerization initiator (c) becomes the compound (a).
Polymerization starts without sufficient chain transfer, and the by-product of a polymer having no hydroxyl group at one or both ends 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, the by-product of the polymer as described above is reduced to a negligible extent, which is more preferable.
A value of 00 or more is most preferable because the by-product of the polymer is reduced to a negligible extent.

In the production method of the present invention, components other than the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c) are substantially not used in the polymerization process. 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 production method of the present invention, particularly in the case of batch type polymerization, compound (a) is added to a polymerization vessel.
At least a part of the required amount of the vinyl monomer (b) and the radical polymerization initiator (c)
Is preferably supplied. One of the reasons why good results were obtained by doing so is as follows. That is, if the polymerization is carried out with at least a part of the required amount of the compound (a) initially charged, the compound (a) is always in a large excess during the polymerization as compared with the radical polymerization initiator (c). Therefore, the radical generated from the radical polymerization initiator (c) is not directly added to the vinyl monomer, but is immediately chain-transferred to the compound (a), and a hydroxyl group is easily formed at the polymer terminal. It is thought that it will be introduced to.

The polymer (I) obtained by the production method of the present invention comprises a vinyl monomer (b) constituting its main chain.
By selecting the type of arbitrarily, transparency, weather resistance,
It has water resistance, hydrolysis resistance, chemical resistance, and various resins such as polyester resin, polyurethane resin, polycarbonate resin, and various block polymers derived from the composition containing the polymer (I). , Very stretchable (good bending workability) and toughness, exhibiting properties such as paints, elastic wall materials, flooring, waterproof coatings, adhesives, tackifiers, adhesives 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 fibers, fiber processing agents, plasticizers, sound absorbing materials, vibration damping materials, surfactants, gel coat agents, resins for artificial marble,
It is very useful as a raw material for an impact resistance imparting agent for artificial marble, a resin for laminated glass, a reactive diluent, and as various resin additives and raw materials thereof.

The polymer (I) is prepared by reacting hydroxyl groups at both ends by an appropriate method to form another functional group (for example, a polymerizable unsaturated group such as a vinyl group, an amino group, a carboxyl group, an 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 containing the polymer (I) and the polyfunctional isocyanate compound (e) as essential components;
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 containing the polymer (I) and the polyfunctional isocyanate compound (e) as essential components is used as a sealing material, it is very soft and tough,
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.

In the process for producing the polymer (II-1) of the present invention, hydroxyl groups can be reliably introduced into both ends of the polymer in the first step as described above. The thus securely introduced hydroxyl groups at both ends are further reacted with a functional group capable of reacting with a hydroxyl group in compound (h) to produce polymer (II-1).
A polymer obtained by reacting the polymer (I) with a compound (h) having two types of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group, in one molecule ( II-1)
In addition, when a composition containing a polymerizable monomer having a polymerizable unsaturated group as an essential component is used for a gel coat resin composition, the reaction shrinkage during molding of the gel coat layer is small, and the work of the gel coat resin composition is performed. The viscosity at the time is low, the gel coat workability is good, and the hardness is large, and a tough and weather-resistant gel coat layer is obtained.

In the method for producing the polymer (II-2) of the present invention, hydroxyl groups can be reliably introduced into both ends of the polymer in the first step as described above. The thus securely introduced hydroxyl groups at both ends are further reacted with a functional group capable of reacting with a hydroxyl group in compound (j) and / or an acid anhydride to produce polymer (II-2). A polyurethane obtained by reacting the polymer (I) with a polyfunctional isocyanate compound (e), and a compound (g) having two or more carboxyl groups in one molecule with the polymer (I). When the polyester obtained by the reaction is used as an essential component of the thermoplastic elastomer, a thermoplastic elastomer having excellent elongation, oil resistance, water resistance, weather resistance, chemical resistance and low-temperature properties can be obtained.

Polyurethane obtained by reacting polymer (I) with polyfunctional isocyanate compound (e), and compound (g) having two or more carboxyl groups in one molecule with polymer (I) When polyesters obtained by reacting with each other are used as essential components of a molding material, a molding material excellent in processability, hydrolysis resistance, weather resistance, chemical resistance and low-temperature properties can be obtained.

[0108]

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. Example 1 A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 153 parts of 2-hydroxyethyl disulfide (compound (a)) and charged with 100 g of nitrogen gas slowly. Heated to ° C. 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 dropwise addition, stirring was continued at the same temperature for another 30 minutes to complete the polymerization, thereby obtaining a dispersion 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 (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.

Examples 2 to 10 In Examples 1, the types and amounts of the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c) are shown in Tables 1 to 3 below. Initially, the entire amount of the compound (a) was initially charged into a flask, and a radical polymerization initiator (c) dissolved in a vinyl monomer (b) was dropped therein over 1 hour, and the dropping was completed. Thereafter, polymers [2] to [10] were obtained in the same manner as in Example 1 except that the polymerization was terminated 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 conversion obtained in the same manner as in Example 1.

Example 11 In Example 5, compound (a) was added to a flask at the beginning of polymerization.
The amount of 2,2'-dithioglycolic acid di (2-hydroxyethyl) ester charged as 30 parts was
A polymer [11] was obtained in the same manner as in Example 5, except that the remaining 240 parts were dropped over 2 hours together with the vinyl monomer (b) in which the initiator (c) was dissolved. Was.

For the obtained polymer [11], the number average molecular weight was measured with a vapor pressure molecular weight measuring device (VPO), and the average number of terminal hydroxyl groups (Fn (OH)) was determined.
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 conversion obtained in the same manner as in Example 1.

Example 12 In Example 2, the types and amounts of the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c), the initially charged amount and the polymerization of the compound (a) were used. The same procedure as in Example 2 was carried out except that the temperature was 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 Example 1.
The results are shown in Table 6 below together with the conversion obtained in the same manner as in the above.

-Examples 13 to 15- A reaction tube equipped with a Sumitomo / Sulzer SMX type element (manufactured by Sulzer) and an external jacket (with an inner diameter of 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. Next, the polymer was purified by the same purification method as in Example 1 to obtain polymers [13] to [15].

The number average molecular weights (Mn) of the purified polymers [13] to [15] were determined 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 results are shown in Table 6 below together with the conversion obtained in the same manner as in Example 1.

Example 16 In 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, A 30% amount of the vinyl-based monomer (b) and the radical polymerization initiator (c) was immediately injected from the third reaction tube to 6.4 ml / p by a plunger pump.
A polymer [16] was obtained in the same manner as in Example 13, except that the mixture was supplied at a flow rate of 1 minute.

The number average molecular weight (Mn) of the purified polymer [16] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and the average number of terminal hydroxyl groups (Fn (OH)) was determined. 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 Example 1.
The results are shown in Table 6 below together with the conversion obtained in the same manner as in the above.

Examples 17 and 18 A twin-screw extruder with an external jacket (1 inch inner diameter, L / L) having another material supply port between the supply port and the take-out port in addition to the material supply port and the product take-out port. D = 48, number of barrels 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 weights (Mn) of the purified polymers [17] and [18] were determined 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 results are shown in Table 7 together with the conversion obtained in the same manner as in Example 1.

Example 19 In Example 17, 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, A 50% amount of the vinyl-based monomer (b) and the radical polymerization initiator (c) was supplied to the raw material supply port at the center of the extruder through a plunger pump at a rate of ml / ml.
A polymer [19] was obtained in the same manner as in Example 17, except that the mixture was continuously supplied at a flow rate of 1 minute.

The number average molecular weight (Mn) of the purified polymer [19] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and the average number of terminal hydroxyl groups (Fn (OH)) was determined. 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 Example 1.
The results are shown in Table 7 below together with the conversion obtained in the same manner as in the above.

-Examples 20 to 22- KRC kneader with an outer jacket provided with a raw material supply port and a product take-out port (inner diameter 2 inches, L / D = 13.2, effective inner volume 1.2 L, Kurimoto Tekko Co., Ltd.) Manufactured by mixing a compound (a), a vinyl monomer (b) and an initiator (c) in the ratio shown in Table 5 at a flow rate of 20 ml / min using a plunger pump. The paddle rotation speed is set to 20 rpm, and the average residence time in the steady state is 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 weights (Mn) of the purified polymers [20] to [22] were determined 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 results are shown in Table 7 together with the conversion obtained in the same manner as in Example 1.

-Example 23-In Example 7, 20 parts (3% by weight of the total) of dioxane was used as a component other than the compound (a), the vinyl monomer (b) and the initiator (c) to obtain the compound (a). Example 7 except that the flask was initially charged 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 with a vapor pressure molecular weight analyzer (VPO), and the average number of terminal hydroxyl groups (Fn (OH)) was determined.
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. Table 7 shows the results together with the conversion obtained in the same manner as in Example 1.
It was shown to.

Comparative Example 1 In Example 1, the amount of AIBN was changed to 4.1 parts (compound (a) / initiator (c) = 40 (molar ratio) in charged composition).
A comparative polymer (1) was obtained in the same manner as in Example 1 except that the above was used. In addition, AI calculated from the residual rate of 2-hydroxyethyl disulfide measured by liquid chromatography and the decomposition rate of AIBN at the polymerization temperature of this comparative example.
From the residual ratio of BN, the molar ratio of the compound (a) and the initiator (c) in the flask at the beginning of the polymerization (= (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 determined in Example 1.
As a result, a result of a number average molecular weight of 2300 and an average number of terminal hydroxyl groups (Fn (OH) of 1.2) was obtained. Comparative Example 2 In Example 14, the amount of AIBN was 32.8 parts. A comparative polymer (2) was obtained in the same manner as in Example 14, except that (compound (a) / initiator (c) = 5 (molar ratio)).

The AIB 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 example.
From the residual rate of N, the molar ratio of the compound (a) and the initiator (c) in the flask (= (a)
/ (C)) was significantly lower than 50.

The number average molecular weight and average number of terminal hydroxyl groups (Fn (OH)) of the obtained comparative polymer (2) were determined in 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 Example 3 A comparative example was prepared in the same manner as in Example 18 except that the amount of AIBN was changed to 32.8 parts (compound (a) / initiator (c) = 5 (molar ratio)). Polymer (3) was obtained.

The AIB 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 example.
From the residual rate of N, the molar ratio of the compound (a) and the initiator (c) in the flask (= (a)
/ (C)) was significantly lower than 50.

The number average molecular weight and the average number of terminal hydroxyl groups (Fn (OH)) of the obtained comparative polymer (3) were determined in 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 Example 4 In Example 1, 100 parts of dioxane was used as a solvent in addition to the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c), and the compound (a) and the vinyl monomer were used. (B) and a radical polymerization initiator (c) in the same manner as in Example 1 except for initial charging in a flask,
A comparative polymer (4) was obtained.

The number average molecular weight and average number of terminal hydroxyl groups (Fn (OH)) of the obtained comparative polymer (4) were determined in 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 Example 5- In Example 14, 100 parts of dioxane was used as a solvent in addition to the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c), and the compound (a) and the vinyl monomer were used. A comparative polymer (5) was obtained in the same manner as in Example 14, except that the mixture mixed together with (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 determined in 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. -Example 24-In Example 1, the amounts of 2-hydroxyethyl disulfide and AIBN were changed to 19.2 parts and 0.1 parts, respectively.
(Compound (a) / vinyl monomer (b) = 0.
3 (wt ratio)) in the same manner as in Example 1 to obtain a polymer [24].

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 Example 1. The number average molecular weight was 23,000 and the average number of terminal hydroxyl groups (Fn (OH)). OH)) of 1.3. -Reference Example 25-The polymer [1] 100 obtained in 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).
8000. -Reference Example 26-In Reference Example 25, instead of 100 parts of the polymer [1], 65 parts of the polymer [1] and 35 parts of the polymer [2] obtained in Example 2 were used, and hexamethylene diisocyanate was used. The same operation as in Reference Example 25 was performed except that the amount was changed to 8.5 parts, to obtain a toluene solution of the 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).
8000. -Reference Example 27-Reference Example 25 is the same as Reference Example 25 except that 50 parts of the polymer [1] and 50 parts of the polymer [2] obtained in Example 2 are used instead of 100 parts of the polymer [1]. The same operation as described above was performed to obtain a toluene solution of polyurethane [27].

The number average molecular weight (Mn) of this polyurethane [27] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
8000. -Reference Example 28-In Reference Example 27, instead of 50 parts of the polymer [2],
The same operation as in Example 27 was carried out except that 37 parts of polymer [3] obtained in Example 3 was used, and polyurethane [28]
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. -Reference Example 29-The same operation as in Reference Example 25 except that 70 parts of polymer [1] and 0.51 part of 1,4-butanediol are used instead of 100 parts of polymer [1]. Was carried out to obtain a toluene solution of polyurethane [29].

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. -Reference 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 Example 2
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 the number average molecular weight, it is considered that an ABA type segment block type polyurethane having the polymer [2] obtained by the production method of the present invention as the component A and the Viron GK130 as the component B is produced. . -Reference Example 31- A flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, a dropping funnel, and a reflux condenser was charged with 100 parts of toluene and 3.5 parts of hexamethylene diisocyanate, and the temperature was raised to 80 ° C. Polymer [2] 4 obtained in 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 Example 1
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.

Reference 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 Example 1, 7.4 parts of phthalic anhydride, 5 parts of xylene was charged, sufficiently stirred, and dewatered from an azeotropic dehydration tube at 100 ° C. for 2 hours, then at 160 ° C. for 2 hours, and finally at 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 gel permeation chromatography (GPC) using a standard polystyrene conversion method.
2000. -Reference Example 33-In Reference Example 32, 65 parts of the polymer [1] and 35 parts of the polymer [2] obtained in Example 2 were used instead of 100 parts of the polymer [1], and phthalic anhydride was used. The same operation as in Reference Example 32 was carried out except that the amount was 7.1 parts, to obtain a polyester [33].

The number average molecular weight (Mn) of this polyester [33] was measured by gel permeation chromatography (GPC) using a standard polystyrene conversion method.
0000. -Reference Example 34-Reference Example 32 is the same as Reference Example 32 except that 50 parts of the polymer [1] and 50 parts of the polymer [2] obtained in Example 2 are used instead of 100 parts of the polymer [1]. The same operation as described above was carried out to obtain a polyester [34].

The number average molecular weight (Mn) of this polyester [34] was measured by standard polystyrene conversion method using gel permeation chromatography (GPC).
8000. -Reference Example 35-The same operation as Reference Example 32 except that in Example 32, 65 parts of polymer [1] and 1.6 parts of 1,4-butanediol are used instead of 100 parts of polymer [1]. Was carried out to obtain a polyester [35].

The number average molecular weight (Mn) of this polyester [35] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC).
5000. -Reference 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.

After cooling, 100 parts of the polymer [12] obtained in Example 12 on the primer coating film, 30 parts of Cymel 325 (manufactured by Mitsui Cyanamid Co., Ltd.) as an alkyl etherified aminoformaldehyde resin, and curing acceleration A mixture of 0.25 part of paratoluenesulfonic acid, 125 parts of titanium oxide, 0.5 part of a leveling agent MK Conc (manufactured by Kyoeisha Yushi Kagaku Kogyo KK), and 400 parts of cyclohexanone, which was thoroughly mixed with a paint shaker, was dried. Apply with a bar coater so that the film thickness becomes 25μ, 70 ° C
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).

The polymer [1] obtained in Example 12 was directly applied to a 0.5 mm-thick galvanized steel sheet which had been subjected to chromate treatment without using the acrylic primer resin.
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.

A: No peeling from the primer substrate (steel plate), good adhesion between the primer and the top coat, and cohesive failure of the top coat only.・ ・ ・: 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 substrate 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 blister, adhesion: 100/100 △: Blister generation ×: Significant blister generation (5) Contact resistance The coated steel plate was cross-cut with a cutter knife to JIS.
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.

Table 8 summarizes the test results. The top coat using a polymer having hydroxyl groups at both ends obtained by the production method of the present invention has excellent adhesion to the primer, is not easily damaged, and is also flexible and excellent in processability, and has boiling water resistance. Also, it was found that the material had excellent touch resistance.

Comparative Reference Examples 6 and 7 In Comparative Example 36, the same operation as in Reference Example 36 was repeated except that the polymer [12] used for the overcoat paint was as shown in Table 8. It was created. Table 8 summarizes the test results of the coating films. -Reference Example 37- Trimethylolpropane obtained by adding 3 equivalents of tolylene diisocyanate to 100 parts of the polymer [17] obtained in Example 17 (Coronate L (manufactured by Nippon Polyurethane), hereinafter referred to as Coronate L) and diluted with ethyl acetate to a 20% solution to give 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.

：: Uniform strength is shown because the peel strength is large and the wrinkles are peeled off. 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 properties (observation results) ：: Uniform application possible ：: Partially repelled ×: Repelled The adhesive composition using a polymer having hydroxyl groups at both ends obtained by the production method of the present invention is: When used as an adhesive for lamination, the adhesive strength was not only high in the initial and normal conditions, but also extremely excellent in hot water resistance, chemical resistance and flexibility.

-Comparative Reference Examples 8 and 9-The same procedure as in Reference Example 37 was repeated except that the polymer shown in Table 9 was used instead of the polymer [17] in Reference Example 37, and a comparative laminate film test was performed. I got a piece. Table 9 shows the evaluation results of the normal adhesion, hot water resistance, chemical resistance and flexibility of the test piece.

Reference Example 38 To 35 parts of the polymer [16] obtained in Example 16, 35 parts of ethyl acetate, 30 parts of toluene and Coronate L (an isocyanate compound manufactured by Nippon Polyurethane Co., Ltd.) were added, and the mixture was stirred well. Thereafter, the composition was coated on a 25 μm thick PET film so that the thickness after drying was 25 μm, and dried by heating at 100 ° C. for 3 minutes to obtain a pressure-sensitive adhesive sheet.

With respect to this pressure-sensitive adhesive sheet, the adhesive force at 23 ° C. and 5 ° C., the initial tack (probe tack) and the adhesive holding force were measured by the following methods, and the results shown in Table 10 were obtained. Adhesive strength : A sample pressure-sensitive adhesive sheet (25 mm width) is reciprocated on a polyethylene plate by one reciprocation of a rubber roller of 2 kg in an atmosphere of a temperature of 23 ° C. and a humidity of 65% and an atmosphere of a temperature of 5 ° C. to paste together. 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 : A test pressure-sensitive adhesive sheet was attached to a probe tack tester (manufactured by Nichiban) in an atmosphere at a temperature of 23 ° C. and a humidity of 65%, and in an atmosphere at a temperature of 5 ° C., and the contact time The resistance value when peeled off at a speed of 1 cm / sec in one second 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, and 80 ° C after 20 minutes.
, A time of 1 kg of load until falling was measured.

The pressure-sensitive adhesive composition using a polymer having hydroxyl groups at both ends obtained by the production method of the present invention has not only excellent adhesive strength at ordinary temperature, probe tack and adhesive holding power, but also excellent In particular, the adhesive strength at low temperatures and probe tack were excellent. -Reference Example 39-The same procedure as in Reference Example 38 was repeated except that the polymer [7] obtained in Example 7 was used instead of 35 parts of the polymer [16] in Reference Example 38, and pressure-sensitive adhesion was performed. I got a sheet.

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

With respect to this comparative pressure-sensitive adhesive sheet, the adhesive strength at 23 ° C. and 5 ° C., the initial tack and the adhesive holding power at 23 ° C. and 5 ° C. were measured, and the results shown in Table 10 were obtained. -Reference Example 40- 100 parts of calcium carbonate, 15 parts of titanium dioxide, 20 parts of calcium oxide, 3PARON 3600N (Kusumoto Chemical Co., Ltd.) were added to 100 parts of the polymer [13] obtained in Example 13.
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.

The elastic sealant composition using a polymer having hydroxyl groups at both ends obtained by the production method of the present invention has not only excellent elongation under normal conditions but also excellent weather resistance. Met. -Reference Example 41-Example 5 in place of the polymer [13] in Reference Example 40.
The same operation as in Reference Example 40 was repeated except that the polymer [5] obtained in the above 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 Reference Examples 11 to 13 The same operation as in Reference Example 40 was repeated, except that the polymer shown in Table 11 was used instead of the polymer [13] in Reference 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.

Reference Example 42 A mixture of 700 parts of the polymer [1] obtained in Example 1 and 6.1 parts of trimethylolpropane was dried by heating at 70 ° C. for 2 hours under a reduced pressure of 2 Torr. . 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 Reference Examples 14 to 16 In Reference Example 42, the same operation as in Reference Example 42 was repeated, except that the polymer of the type and amount shown in Table 12 was used instead of 700 parts of the polymer [1]. A comparative flexible urethane foam was obtained. The physical properties are shown in Table 12. -Example 43-(Synthesis of polymer having polymerizable unsaturated groups at both ends) 100 parts of the polymer [21] obtained in Example 21 in a flask equipped with a stirrer, a reflux condenser and a thermometer, anhydrous After charging 5.6 parts of maleic acid, 0.1 part of dibutyltin oxide, 0.1 part of hydroquinone and 200 parts of toluene, stirring at 100 ° C. for 5 hours and performing a reaction, toluene was removed by an evaporator and a reduced-pressure dryer. Thus, a polymer [43] was obtained.

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

-Reference Examples 45 to 49-Using the polymers [43] and [44] obtained in Examples 43 and 44, gel coat resin compositions were prepared in the proportions 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 were 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 Reference 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 B: Almost no change C: Slightly swells D: Swells when swelled Thermoplastic elastomers using polyurethane and polyester not only have large elongation under normal conditions, but also have oil resistance , Weather resistance, chemical resistance and the like.

Reference Example 51 The same evaluation as in Reference Example 50 was carried out, except that the polyurethane [31] obtained in Reference Example 31 was used instead of the polyurethane [26] obtained in Reference 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 Reference Example 26. Table 14 shows the obtained results.

Comparative Examples 17 and 18 In Reference Example 50, the same operations as in Reference Example 50 were repeated except that the polymers shown in Table 14 were used instead of the polyurethane [26] obtained in Reference Example 26, and An evaluation test was conducted on a thermoplastic elastomer as a comparative polymer. Table 14 shows the results.

-Reference Examples 53 and 54-The polyurethane [27] obtained in Reference Example 27 and the polyester [34] obtained in Reference Example 34 were subjected to evaluation tests 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 characteristics Regarding the low temperature characteristics, the obtained polyurethane (polyester) pellet was heated at 250 ° C. 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 processability and excellent not only low-temperature properties but also very good hydrolysis resistance and weather resistance. -Comparative Reference Examples 19 and 20-In Reference Example 53, an evaluation test on the molding material was performed using the polymers shown in Table 15 instead of the polyurethane [27] obtained in Reference Example 27, and the results were obtained. Table 15 summarizes the results.

[0180]

[Table 1]

[0181]

[Table 2]

[0182]

[Table 3]

[0183]

[Table 4]

[0184]

[Table 5]

[0185]

[Table 6]

[0186]

[Table 7]

The notes in 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.

[0188]

[Table 8]

[0189]

[Table 9]

[0190]

[Table 10]

[0191]

[Table 11]

[0192]

[Table 12]

[0193]

[Table 13]

[0194]

[Table 14]

[0195]

[Table 15]

Reference Example 55 The polymer [1] 100 obtained in 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 Reference Example 21-The same operation as in Reference Example 55 was repeated, except that in place of the polymer [1], a conventionally known polyester polyol having a number-average molecular weight (Mn) = 2,000 was used. Polyurethane [21] was obtained.

-Comparative Reference Example 22-The same operation as in Reference Example 55 was carried out except that in place of the polymer [1], a conventionally known polyether polyol having a number average molecular weight (Mn) = 3,000 was used. This was repeated to obtain a comparative polyurethane [22]. -Reference Example 56 and Comparative Reference Examples 23 to 24-The polyurethane [55] obtained in Reference Example 55 and the comparative polyurethane [2] obtained in Comparative Reference Examples 21 to 22
With respect to 1] to [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 Polyurethane [55] 100% Comparative Polyurethane [21] 80% (2) Heat Resistance The heat resistance of the polyurethane [55] and the 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 Polyurethane [55] 100% Comparative Polyurethane [22] The shape of the film was not retained. -Reference Example 57-In a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 760 parts of the polymer [4] obtained in Example 4 and 66.7 parts of isophorone diisocyanate were mixed, 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 above 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. 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 off without any 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 Reference Example 25-The same operation as in Reference Example 57 was performed except that 300 parts of a conventionally known polytetramethylene glycol having a number average molecular weight (Mn) = 2,000 was used instead of the polymer [4]. A comparative printing ink composition comprising polytetramethylene glycol was repeatedly obtained, and the printability and durability of this composition were examined in the same manner as in Reference Example 57. Table 16 shows the results.

Comparative Reference Example 26 In Reference Example 57, 300 parts of a conventionally known polybutylene adipate diol having a number average molecular weight (Mn) of 2,000 was replaced with 300 parts of 4,4-dicyclohexylmethane in place of the polymer [4]. The same operation as in Reference Example 57 was repeated, except that 79 parts of diisocyanate was used, to obtain a comparative printing ink composition composed of polytetramethylene glycol. The durability was examined. Table 16 shows the results.

[0207]

[Table 16]

-Example 58- (Example relating to thermosetting polyurethane elastomer composition) [0208] In the same manner as in Example 1, except that instead of 64 parts of butyl acrylate, 43 parts of methyl acrylate were used. To obtain a number average molecular weight of 2,200, Fn
A polymer [58] having (OH) = 2.0 was obtained.

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

1660 parts of the obtained reaction product was degassed under reduced pressure at 80 ° C., and was 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 polyurethane elastomer [59] was examined for stress-strain characteristics (by Instron) and durability.
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 Reference Example 27-(Comparative Reference Example Regarding Thermosetting Polyurethane Elastomer Composition) In Reference Example 59, instead of the polymer [58], a conventionally known polyester having a number average molecular weight (Mn) = 1,000 was used. The same operation as in Reference Example 59 was repeated, except that 552 parts of the polyol were used, to obtain a polyurethane elastomer [2
7].

This comparative polyurethane elastomer [2
7] was examined in the same manner as in Reference Example 59. Table 17 shows the results. -Comparative Reference Example 28-(Comparative Reference Example Regarding Thermosetting Polyurethane Elastomer Composition) In Reference Example 59, a conventionally known polyether polyol having a number average molecular weight (Mn) = 1,000 was used instead of the polymer [58]. The same operation as in Reference Example 59 was repeated, except that 552 parts were used, to give a comparative polyurethane elastomer [2
8] was obtained.

This comparative polyurethane elastomer [2
8] was examined in the same manner as in Reference Example 59. Table 17 shows the results.

[0215]

[Table 17]

-Reference Example 60- (Reference Example Regarding Resin Composition for Floor Material) In a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 85 parts of the polymer [1] of Example 1 and TDI were added.
8.3 parts were added and reacted while stirring at 80 ° C. for 3 hours in a nitrogen stream to obtain a polymer [1] / TDI prepolymer.

Next, using this polymer [1] / TDI prepolymer, a polyurethane composition (flooring resin composition) having a composition shown in Table 18 was produced.
Measures surface adhesion and durability (hydrolysis resistance and heat resistance)
evaluated. Table 19 shows the results. -Comparative Reference Example 29- (Comparative Reference Example Regarding Resin Composition for Floor Material) In a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 85 parts of polypropylene glycol having a number average molecular weight of 2,000 and TDI15 were added. Then, the mixture was reacted at 80 ° C. for 3 hours with stirring in a nitrogen stream to obtain a polypropylene glycol / TDI prepolymer.

Next, the 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 Reference Example 30-A flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser was charged with 85 parts of a polyester polyol having a number average molecular weight of 2,000 and 15 parts of TDI, and heated at 80 ° C in a nitrogen stream. The mixture was reacted with stirring for 3 hours to obtain a polyester polyol / TDI prepolymer.

Next, the 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.

[0220]

[Table 18]

[0221]

[Table 19]

-Example 61- (Synthesis of polymer having polymerizable unsaturated groups at both ends) Except that in Example 43, 116 parts of polymer [1] was used instead of 100 parts of polymer [21]. The same operation as in Example 43 was repeated to obtain a polymer [61]. -Example 62-(Synthesis of polymer having polymerizable unsaturated groups at both ends) Example 43 was repeated except that in place of 100 parts of polymer [21], 116 parts of polymer [2] was used. The same operation as described above was repeated to obtain a polymer [62].

-Example 63- (Synthesis of polymer having polymerizable unsaturated groups at both ends) Except for using 452 parts of polymer [6] in place of 100 parts of polymer [21] in Example 43, The same operation as in Example 43 was repeated to obtain a polymer [63]. -Example 64-(Synthesis of polymer having a polymerizable unsaturated group at both ends) Example 43 was repeated except that 65 parts of polymer [10] was used instead of 100 parts of polymer [21]. The same operation as described above was repeated to obtain a polymer [64].

Reference Example 65 50 parts of the polymer [62] obtained in 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., which was cured in 30 minutes, and further 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 A cured product was obtained in the same manner as in Reference Example 65, except that the 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 (Higilite 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 shown in Table 23, the physical properties of the obtained cured product had a problem in impact resistance. -Comparative Reference Example 32-As shown in Table 22, the same as Reference Example 65 except that 20 parts of ethylene glycol dimethacrylate was used instead of 50 parts of a polymer having polymerizable unsaturated groups at both ends [62]. 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 (Higilite 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.

Next, this composition was mixed with 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 the resin composition 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.

[0234]

[Table 20]

[0235]

[Table 21]

[0236]

[Table 22]

[0237]

[Table 23]

-Example 70- (Synthesis of polymer having carboxyl group at both ends) In a flask equipped with a stirrer, a reflux condenser and a thermometer,
100 parts of the polymer [1] obtained in Example 1, 5.5 parts of maleic anhydride, and 2.8 parts of triethylamine were charged, and 8
The mixture was stirred at 0 ° C. for 6 hours to obtain a polymer [70].

The physical properties of the polymer [70] were such that the number average molecular weight (Mn) was 3,800 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. -Example 71-(Synthesis of polymer having carboxyl groups at both ends) In a flask equipped with a stirrer, a reflux condenser and a thermometer,
8 parts were charged with 100 parts of the polymer [13] obtained in Example 13, 5.0 parts of succinic anhydride, and 2.1 parts of sodium acetate.
The mixture was stirred at 0 ° C. for 6 hours to obtain a polymer [71].

The physical properties of the polymer [71] were such that 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 number average molecular weight determined by titration with alcoholic KOH. From this, it is considered that the reaction proceeded quantitatively. -Example 72- (Synthesis of polymer having carboxyl groups at both ends) In a flask equipped with a stirrer, a reflux condenser and a thermometer,
100 parts of the polymer [14] obtained in Example 14, 5.9 parts of phthalic anhydride, and 2.0 parts of triethylamine were charged.
The mixture was stirred at 80 ° C. for 6 hours to obtain a polymer [72].

The physical properties of the polymer [72] were such that the number average molecular weight (Mn) was 5100 as measured by GPC, and the number of terminal carboxyl groups (Fn (COOH)) was 1.9 based on the titration with alcoholic KOH and the above number average molecular weight. From this, it is considered that the reaction proceeded quantitatively. -Example 73-(Synthesis of polymer having carboxyl group at both terminals and side chains) In a flask equipped with a stirrer, a reflux condenser and a thermometer,
100 parts of the polymer [17] obtained in Example 17, 0.7 part of itaconic anhydride and 0.3 part of triethylamine were charged and stirred at 90 ° C. for 6 hours to obtain a polymer [73].

The physical properties of the polymer [73] were as follows: the number average molecular weight (Mn) was 16,000 as measured by GPC, and the polymer 1 was determined by titration with alcoholic KOH and the above number average molecular weight.
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 Example 70 was mixed with an epoxy resin and a curing agent in the ratio shown in Table 24 to obtain an epoxy resin composition.

The epoxy resin composition was subjected to an adhesion test and a heat resistance test. 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 Example 70 and the epoxy resin were preliminarily heated 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], Hibe CTBN 130 manufactured by Ube Industries 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 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.

[0246]

[Table 24]

[0247]

According to the process for producing a polymer having hydroxyl groups at both ends (polymer (I)) according to the present invention, the polymerization of the vinyl monomer (b) in the presence of the compound (a) is carried out. When the reaction is carried out using the radical polymerization initiator (c), the compound (a) is always present in the reactor at 50 mole times or more of the initiator (c) during the reaction. ),
In order not to use anything other than (c),
Hydroxyl groups, which are reactive groups at both ends of the polymer, are introduced easily, reliably, and efficiently, resulting in polymers having hydroxyl groups at both ends, including polar vinyl monomers. It is possible to obtain easily and inexpensively and efficiently from a wide range of vinyl monomers.

The polymer (I) obtained by this production method has various hydroxyl groups at both ends, and thus, itself, various resins such as polyester resins, polyurethane resins and polycarbonate resins, various block polymers, paints, and elastic walls. Materials, waterproof coating materials, floor materials, adhesives, tackifiers, adhesives, binders, sealing materials, urethane foam (hard, semi-rigid, 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.

The polymer (I) comprising, as essential components, a polymer (I) obtained by the production method of the present invention and a polyfunctional compound (d) having two or more functional groups capable of reacting with a hydroxyl group in one molecule. I) The composition includes various resins such as polyester resin, polyurethane resin, and polycarbonate resin, various block polymers, paints, elastic wall materials, waterproof coating materials, adhesives, flooring materials, tackifiers, adhesives, and binders. (Magnetic recording media, ink binder, casting binder,
Fired brick binder, graft material, microcapsule, glass fiber sizing, etc.), sealing material,
Urethane foam (hard, semi-hard, soft), urethane R
IM, high solid paint, thermosetting elastomer, thermoplastic elastomer, microcellular, artificial leather, synthetic leather, elastic fiber, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, artificial marble, resin for ink, film ( Laminating adhesives, protective films, etc.), as a raw material for reactive diluents, etc., and when used in various resin additives and their raw materials, etc., they not only have soft and tough mechanical properties,
Depending on the type of the monomer component (b) constituting the main chain of the polymer (I), very good physical properties such as transparency, weather resistance, water resistance, hydrolysis resistance, and chemical resistance are also regrettable. Demonstrate and show very good physical properties.

For example, a low molecular weight polymer having a weight average molecular weight of about 1,000 to 10,000 is used as the polymer (I), and this is combined with a bifunctional isocyanate compound or the like to extend the chain after coating on a substrate. , When used as an adhesive, compared with a conventional polymer obtained by copolymerizing a vinyl monomer having a functional group (usually one having a weight average molecular weight of 100,000 or more is used) Thus, the viscosity of the pressure-sensitive adhesive composition is low, so that the amount of solvent used can be reduced, 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 polymer (I) -containing composition is used for an adhesive composition, the composition contains, as one of the essential components, the polymer (I) obtained by the production method of the present invention. Therefore, compared to the case of using an acrylic polymer obtained by copolymerizing a vinyl monomer having a functional group, if the same adhesive performance is obtained, the viscosity of the adhesive composition is low, and therefore In addition, effects not available in the conventional adhesive composition, such as reduction in the amount of solvent used and improvement in workability, can be obtained. In addition, the adhesive using the polymer (I) -containing composition has excellent heat resistance as compared with the adhesive using the currently used polyether polyol, and uses the currently used polyester polyol. Hydrolysis resistance is superior to that of the adhesive.

When the composition containing the polymer (I) is used for artificial leather compositions and / or synthetic leather compositions, a polymer having hydroxyl groups at both ends is used in combination with a conventionally known isocyanate compound or the like. Hydrolysis resistance,
The heat resistance and the weather resistance have effects which are not provided by the conventional artificial leather composition and / or synthetic leather composition. Further, the artificial leather composition and / or the synthetic leather composition using the polymer (I) -containing composition are compared with the artificial leather composition and / or the synthetic leather composition using the currently used polyether polyol. As well as excellent heat resistance, and excellent hydrolysis resistance as compared with artificial leather compositions and / or synthetic leather compositions using polyester polyols currently used.

When the composition containing the polymer (I) is used for the application of a thermosetting polyurethane elastomer composition, the polymer (I) is used in combination with a conventionally known isocyanate compound and the like, so that the hydrolysis resistance and the heat resistance are improved. In addition, an effect which is not provided by the conventional thermosetting polyurethane elastomer composition in light deterioration resistance can be obtained. Further, the polymer (I)
The thermosetting polyurethane elastomer composition using the containing composition has excellent heat resistance compared with the thermosetting polyurethane elastomer composition using the currently used polyether polyol, and the polyester polyol currently used is It is excellent in hydrolysis resistance as compared with a thermosetting polyurethane elastomer composition using the same, and is superior in light deterioration resistance as compared with a thermosetting polyurethane elastomer composition using a polycarbonate polyol currently used.

When the composition containing the polymer (I) 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, An effect which is not provided by the conventional resin composition for flooring in light deterioration resistance is obtained. Further, the resin composition for flooring using the polymer (I) -containing composition has excellent heat resistance as compared with the resin composition for flooring using polyether polyol currently used. Hydrolysis resistance is superior compared to resin compositions for flooring materials using polyester polyols, and light degradation resistance is superior to resin compositions for flooring materials using polycarbonate polyols currently used. ing.

When the composition containing the polymer (I) is used for a printing ink composition, the polymer (I) is used in combination with a conventionally known isocyanate compound and the like, so that hydrolysis resistance, heat resistance and weather resistance are used. In this case, an effect which has not been obtained in the conventional printing ink composition can be obtained. Further, the polymer (I)
The printing ink composition using the containing composition has better heat resistance than the printing ink composition using the currently used polyether polyol, and the printing ink composition using the currently used polyester polyol. Hydrolysis resistance is superior to the product.

When the composition containing the polymer (I) is used for urethane foam, the polymer (I) is used in combination with a conventionally known isocyanate compound and the like, so that flexibility, weather resistance, heat resistance, water resistance, In terms of chemical resistance and rebound resilience, an effect not obtained by the conventional urethane foam composition can be obtained. Further, the urethane foam using the polymer (I) -containing composition has excellent heat resistance as compared with the urethane foam using the currently used polyether polyol, and the polyester polyol currently used is used. It has better hydrolysis resistance than urethane foam. In the currently marketed acrylic polyol having the effect of the main chain being an acrylic ester,
Since it is a copolymer with hydroxyethyl acrylate, 1
Since there is a polymer containing three or more hydroxyl groups in the molecule, it is impossible to produce a thermoplastic polyurethane indispensable for artificial leather and synthetic leather.

When the polymer (I) -containing composition is used for a sealing material, the polymer (I) is combined with a conventionally known isocyanate compound to be flexible and tough, and to have weather resistance, heat resistance and water resistance. In addition, an effect which is not provided by the conventional sealing material composition in terms of chemical resistance and rebound resilience is obtained. Further, a sealing material using the polymer (I) -containing composition has excellent heat resistance as compared with a sealing material using a currently used polyether polyol.

In the method for producing a polymer having polymerizable unsaturated groups at both terminals (polymer (II-1)) according to the present invention,
The polymer (I) obtained by the above-mentioned production method is reacted with a compound (h) having two types of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group in one molecule. Therefore, a polymerizable unsaturated group, which is a reactive group, is easily, reliably and efficiently introduced into both ends of the polymer. As a result, the polymer (II-1) is converted into a polar vinyl-based polymer. It is possible to obtain easily and inexpensively and efficiently from a wide range of vinyl monomers including monomers.

In addition to the polymer (II-1) thus obtained, a gel coat resin composition comprising a composition containing, as an essential component, a vinyl monomer having one polymerizable unsaturated group in one molecule. When used in artificial marble resin compositions, laminated glass resin compositions, etc., reaction shrinkage during molding is small, viscosity during work is low, workability is good, and the hardness of the cured product is large, tough. And a resin having good weather resistance is obtained.

The artificial marble obtained from the resin composition for artificial marble has excellent heat resistance and weather resistance, and the use of the polymer (II-1) allows the present composition to have a small shrinkage due to polymerization during molding. Thus, problems such as generation of cracks during molding can be 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. Also,
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 polymerization shrinkage at the time of polymerization and to impart flexibility to a molded product, unlike the case where a thermoplastic polymer having no polymerizable unsaturated group, which has been conventionally used, is added. Since the polymer to be polymerized has polymerizable unsaturated groups at both ends, it is incorporated into the crosslinked structure even after molding, so even if the added amount is increased, there is no problem such as a decrease in heat resistance, and the flexibility is also high. Is also sufficiently provided.

The polyurethane obtained by reacting the polymer (I) with the polyfunctional isocyanate compound (e), and the polymer (I) having two or more carboxyl groups in one molecule (g) When used as a thermoplastic elastomer or a molding material, the polyester obtained by reacting with a vinyl monomer having not only soft and tough mechanical properties but also a main chain of a polymer having hydroxyl groups at both ends is obtained. Very good transparency, depending on the type of body component (b),
It is a very useful material that exhibits physical properties such as weather resistance, water resistance, hydrolysis resistance, oil resistance, and chemical resistance without regret, and shows very good physical properties.

In the method for producing a polymer having carboxyl groups at both ends (polymer (II-2)) according to the present invention,
Compound (j) and / or acid anhydride having two types of reactive groups, a functional group capable of reacting with a hydroxyl group and a carboxyl group, in one molecule in the polymer (I) obtained by the above-mentioned production method. , A carboxyl group, which is a reactive group, is introduced into both ends of the polymer easily, reliably, and efficiently. As a result, the polymer (II-2) is converted into a polar vinyl-based polymer. It is possible to obtain easily and inexpensively and efficiently from a wide range of vinyl monomers including monomers.

The polymer (II-2) has the same transparency and weather resistance as the polymer (I) by arbitrarily selecting the type of the vinyl monomer (b) constituting the main chain. ,water resistant,
It has hydrolysis resistance and chemical resistance, and is a polymer (II-2)
Various resins, such as polyesters, derived from polyester, exhibit the properties of being very stretchable (bending processability is good) and tough, so that paints, adhesives, thermoplastic elastomers, various molding materials, Resin modifier (impact-resistant material), vibration damping material, elastic wall material, flooring material, textile material, UV /
It is useful as a raw material for EB cured resins and the like. Further, the polymer (II-2) has a feature that it can be used as a curing agent and an additive for an epoxy resin, which has been difficult to use at a hydroxyl group terminal.

Next, a resin composition comprising, as essential components, a polymer (II-2) and a compound (l) having at least two functional groups capable of reacting with a carboxyl group in one molecule. As in the case of the composition containing the polymer (I), transparency, weather resistance, water resistance, and water resistance can be attained by arbitrarily selecting the type of the vinyl monomer (b) constituting the main chain. Various resins such as polyester derived from a composition containing the polymer (II-2) have decomposability and chemical resistance, and have very high elongation (good bending workability) and toughness. Paints, adhesives, thermoplastic elastomers, various molding materials, resin modifiers (impact imparting materials), vibration damping materials, elastic wall materials, flooring materials, textile materials, UV
-It is useful as a raw material for EB cured resin and the like. Further, the composition containing the polymer (II-2) has a feature that it can be used for an epoxy resin composition which has been difficult to use at a hydroxyl group terminal.

In an epoxy resin composition containing the polymer (II-2) as an essential component, the polymer (II-2)
By adding to the epoxy resin as a rubber component, the toughness is improved, and the effects of heat resistance and weather resistance that are not provided by the conventional epoxy resin composition can be obtained. That is, the epoxy resin composition using the polymer having the polymer (II-2) has higher heat resistance and weather resistance than the currently used epoxy resin composition containing polybutadiene polyol or polybutadiene / acrylonitrile polyol. Are better.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Ikeuchi 5-8 Nishiburi-cho, Suita-shi, Osaka Inside Nippon Shokubai Central Research Laboratory Co., Ltd. No. Nippon Shokubai Central Research Laboratory

Claims (6)

(57) [Claims] 1. The following general formula (1): HO—A— (S) x —B—OH (1) wherein A and B each represent a divalent organic group, and 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 is characterized in that the above-mentioned polymerization is carried out so as to be present in an amount of 0 mol times or more and using substantially no compound other than the compound (a), the vinyl monomer (b) and the radical polymerization initiator (c). And a method for producing a polymer having hydroxyl groups at both ends. 2. The weight ratio of the compound (a) to the vinyl monomer (b) (compound (a) / vinyl monomer (b)) is 0.1.
The method for producing a polymer having hydroxyl groups at both ends according to claim 1, wherein the number is 5 or more. 3. The weight ratio of the compound (a) to the vinyl monomer (b) in the reactor (compound (a) / vinyl monomer (b)) is always 0.5 or more during the reaction. The method for producing a polymer having hydroxyl groups at both ends according to claim 1. 4. At the time of performing polymerization, at least a part of the compound (a) is charged in a reactor in advance, and a vinyl monomer (b) and a radical polymerization initiator (c) are added thereto. The method for producing a polymer having hydroxyl groups at both ends according to any one of claims 1 to 3 , wherein the polymerization is performed while the polymerization is performed. 5. The following general formula (1): HO-A- (S) x -B-OH (1) wherein A and B each represent a divalent organic group, and x
Is an integer of 2 to 5. The compound (a) represented by
In the presence, the polymerization of vinyl monomer (b) is initiated by radical polymerization.
In the method using the initiator (c), the reaction is carried out in a reactor.
The compound (a) is always reacted with the radical polymerization initiator (c) 5
Compound (a), vinyl
Other than the monomer (b) and the radical polymerization initiator (c)
Both ends obtained by performing the above-mentioned polymerization without substantially using
The polymer (I) having a hydroxyl group at one end has a hydroxyl group in one molecule.
Types of reaction between a functional group capable of reacting with a polymer and a polymerizable unsaturated group
Reacting the compound (h) having an ionic group together.
Of polymers having polymerizable unsaturated groups at both ends
Construction method. 6. The following general formula (1): HO-A- (S) x -B-OH (1) wherein A and B each represent a divalent organic group, and x
Is an integer of 2 to 5. The compound (a) represented by
In the presence, the polymerization of vinyl monomer (b) is initiated by radical polymerization.
In the method using the initiator (c), the reaction is carried out in a reactor.
The compound (a) is always reacted with the radical polymerization initiator (c) 5
Compound (a), vinyl
Other than the monomer (b) and the radical polymerization initiator (c)
Both ends obtained by performing the above-mentioned polymerization without substantially using
The polymer (I) having a hydroxyl group at one end has a hydroxyl group in one molecule.
Reactivity between functional group and carboxyl group that can react with
(J) and / or acid anhydride having a group in combination
At both ends.
A method for producing a polymer having a boxyl group.