CN110325563B - Polymer composition containing modified chlorinated polyolefin and method for producing same - Google Patents

Polymer composition containing modified chlorinated polyolefin and method for producing same Download PDF

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CN110325563B
CN110325563B CN201880013006.9A CN201880013006A CN110325563B CN 110325563 B CN110325563 B CN 110325563B CN 201880013006 A CN201880013006 A CN 201880013006A CN 110325563 B CN110325563 B CN 110325563B
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chlorinated polyolefin
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meth
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CN110325563A (en
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小畑政示
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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Abstract

The present invention provides a method for producing a polymer composition containing a modified chlorinated polyolefin, which has excellent stability, and a coating material containing the polymer composition containing a modified chlorinated polyolefin. A polymer composition containing a modified chlorinated polyolefin is obtained by copolymerizing a chlorinated polyolefin (b) having an allyloxy group and a polymerizable monomer containing at least 1 compound (c) selected from the group consisting of (meth) acrylic acid esters, (meth) acrylic acid and styrene in the coexistence of a compound (a) having an allyloxy group and a hydroxyl group.

Description

Polymer composition containing modified chlorinated polyolefin and method for producing same
Technical Field
The present invention relates to a polymer composition containing a modified chlorinated polyolefin, a method for producing the same, and a coating composition containing the same.
Background
Plastic materials are now used in various industrial fields, and among them, polyolefin resins such as polypropylene resins are widely used as substrates for molded articles, films and the like because they have many excellent properties and are economical. However, since polyolefin-based substrates have low polarity and thus have poor adhesion to coating films formed during coating, compositions containing modified chlorinated polyolefins such as acrylic-modified chlorinated polyolefins, which are intended to achieve both adhesion to such polyolefin-based substrates and compatibility with other resin components used in combination, are useful as coatings or primers when coating such plastic substrates such as polyolefins.
As a method for obtaining a composition containing such a modified chlorinated polyolefin, for example, the following methods have been disclosed: a method of introducing a polymerizable unsaturated group by reacting a hydroxyl group-containing polymerizable unsaturated monomer with a chlorinated polyolefin having an acid anhydride group, and polymerizing the polymerizable unsaturated monomer on the polymerizable unsaturated group (patent document 1 and patent document 2).
However, such a conventional technique has the following problems: there are cases where the production stability is insufficient.
Patent document 3 describes, as a method for improving the production stability, a production method including: that is, a method for producing a modified chlorinated polyolefin resin composition, which comprises modifying a chlorinated polyolefin having an acid anhydride group with a hydroxyl group-containing (meth) acrylate and an alcohol, and copolymerizing a polymerizable vinyl monomer in an organic solvent in the presence of the obtained esterified chlorinated polyolefin. However, in the modified chlorinated polyolefin resin composition obtained by the production method, there is a case where curability is insufficient in a composition using a crosslinking agent reactive with a hydroxyl group. In addition, in this production method, production stability may be insufficient.
Documents of the prior art
Patent document
Patent document 1: japanese unexamined patent publication No. 8-59757
Patent document 2: japanese unexamined patent publication No. 2002-309161
Patent document 3: japanese laid-open patent publication No. 2015-3991
Disclosure of Invention
Problems to be solved by the invention
The present invention intends to provide a method for obtaining a polymer composition containing a modified chlorinated polyolefin, which is a method excellent in production stability. Further, in one embodiment of the present invention, there is provided a method for obtaining a polymer composition containing a modified chlorinated polyolefin, which can obtain a composition having excellent curability when used in combination with a crosslinking agent having reactivity with a hydroxyl group.
Means for solving the problems
Namely, the present invention is as follows: a polymer composition containing a modified chlorinated polyolefin is obtained by copolymerizing a chlorinated polyolefin having an allyloxy group with a polymerizable monomer such as an acrylic monomer in the presence of a compound having an allyloxy group and a hydroxyl group.
Effects of the invention
It has been found that, in the case where a polymer composition containing a modified chlorinated polyolefin is obtained by copolymerizing a chlorinated polyolefin having an allyloxy group and a polymerizable monomer such as an acrylic monomer in the presence of a compound having an allyloxy group and a hydroxyl group as in the present invention, the production stability is excellent. Further, it has been found that a polymer composition containing a modified chlorinated polyolefin produced by the production method of the present invention can be obtained as a composition having excellent curability by using a crosslinking agent reactive with a hydroxyl group in combination.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
[ Compound (a) having allyloxy group and hydroxyl group ]
In the present invention, a chlorinated polyolefin (b) having an allyloxy group and a polymerizable monomer containing at least 1 compound (c) selected from the group consisting of (meth) acrylate, (meth) acrylic acid and styrene are copolymerized in the coexistence of a compound (a) having an allyloxy group and a hydroxyl group. The compound (a) having an allyloxy group and a hydroxyl group used in the present invention has an allyloxy group and a hydroxyl group in 1 molecule, and examples thereof include compounds represented by the general formula (I);
Figure BDA0002173612280000031
(in the formula, R1And R2Each independently represents a branched alkylene group having 2 or 3 carbon atoms, m and n each independently represent a real number of 0 to 50, and the sum of m and n represents a real number of 1 or more, and may have a block structure or a random structure. )
An addition reactant of an allyl alcohol and a lactone; and addition reaction products of a compound represented by the general formula (I) and a lactone. Among them, the compound represented by the above general formula (I) is preferred because it is easily available. Specific examples of the compound included in the general formula (I) include allyloxyethanol, ethylene glycol monoallyl ether, and diethylene glycol monoallyl ether, and examples thereof include 2-allyloxyethanol (otherwise referred to as ethylene glycol monoallyl ether), diethylene glycol monoallyl ether, 1-allyloxy-2-propanol (otherwise referred to as propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, polyethylene glycol monoallyl ether, polypropylene glycol (2-allyloxyethyl) ether, and addition reaction products of allyl alcohol with ethylene oxide and propylene oxide.
As the method for producing the compound represented by the general formula (I), a known method can be used, and for example, a method can be used which can be obtained by reacting ethylene oxide and/or propylene oxide with allyl alcohol, or by reacting 1 or more selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol with allyl chloride or allyl alcohol. In these reactions, a basic compound and/or an acidic compound may be present as needed, and these compounds may be neutralized or removed after the reaction is completed.
[ chlorinated polyolefin (b) having allyloxy group ]
The chlorinated polyolefin (b) having an allyloxy group can be obtained, for example, by modifying a chlorinated polyolefin with a compound having a allyloxy group to introduce an allyloxy group. As a method of introducing an allyloxy group to a chlorinated polyolefin, specifically, for example, the following method can be used: a method in which a chlorinated polyolefin having an acid group is reacted with a compound having an allyloxy group and a hydroxyl group, and the compound having the allyloxy group and the hydroxyl group is added to the chlorinated polyolefin through an ester condensation reaction of the acid group and the hydroxyl group; and a method in which the chlorinated polyolefin (d) having an acid anhydride group is reacted with a compound having an allyloxy group and a hydroxyl group, and the compound having an allyloxy group and a hydroxyl group is added to the chlorinated polyolefin through an addition reaction of the acid anhydride group and the hydroxyl group.
As the chlorinated polyolefin having an acid group described above, there can be suitably used: the modification and chlorination may be carried out by a known method, for example, a polyolefin obtained by modifying a polyolefin with an organic carboxylic acid such as maleic acid or itaconic acid to introduce an acid group and then chlorinating the modified polyolefin, or a chlorinated polyolefin obtained by chlorinating a polyolefin with an organic carboxylic acid such as maleic acid or itaconic acid to introduce an acid group. As the chlorinated polyolefin (d) having an acid anhydride group, there can be suitably used: the modification and chlorination may be carried out by a known method, for example, a polyolefin obtained by modifying a polyolefin with an acid anhydride of an organic carboxylic acid such as maleic acid or itaconic acid to introduce an acid anhydride group and then chlorinating the modified polyolefin, or a chlorinated polyolefin obtained by chlorinating a polyolefin with an acid anhydride of an organic carboxylic acid such as maleic acid or itaconic acid to introduce a product (d) of an acid anhydride group. The polyolefin as a raw material is not particularly limited, and is preferably a homo-or copolymer of 1 or more kinds selected from α -olefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene, 1-octene, etc., and a copolymer of these α -olefins and other polymerizable monomers such as vinyl acetate, etc. Among these polymerizations, a Ziegler Natta type catalyst, a metallocene type catalyst and/or a radical initiator may be used, and as a polymerization form, 1-step polymerization or multi-step polymerization may be used, and polymerization of a reactive rubber may be used. These polyolefins may be mixed and used as a raw material for adjusting compatibility, crystallinity, hardness, liquid stability, adhesion, and the like. Examples of the chlorinated polyolefin (d) having an acid anhydride group include "スーパークロン 892L", "スーパークロン 892 LS", "スーパークロン 822", "スーパークロン 822S", "スーパークロン 930", "スーパークロン 930S", "スーパークロン 842 LM", "スーパークロン 851L", "スーパークロン 3228S", "スーパークロン 3221S" and "スーパークロン 2319S" (trade name, maleic anhydride-modified chlorinated polyolefin available from Nippon paper-making Co., Ltd), "ハードレン CY-9122P", "ハードレン CY-9124P", "ハードレン HM-21P", "ハードレン CY-1321P", "ハードレン CY-2121P", "ハードレン CY-2129P"), Commercially available products such as "ハードレン F-225P", "ハードレン F-7P", "ハードレン M-28P", "ハードレン F-2P", "ハードレン F-6P" and "ハードレン CY-1132" (trade name, maleic anhydride-modified chlorinated polyolefin available from Toyo Boseki Co., Ltd.). They may be solution or solid preparations. The chlorinated polyolefin (d) having an acid anhydride group may be used singly or in combination of 2 or more for adjusting compatibility, crystallinity, hardness, liquid stability, adhesion, and the like. The chlorinated polyolefin (d) having an acid anhydride group preferably has a chlorine content of 10 to 35% by mass.
The production process of the present invention has high production stability even when the chlorinated polyolefin (d) having an acid anhydride group has a high chlorine content. Therefore, particularly suitable in the production method of the present invention are: the chlorinated polyolefin (d) having an acid anhydride group has a chlorine content of 10 to 35% by mass, preferably 19 to 32% by mass, and more preferably 20 to 28% by mass. When the chlorine content is more than 35% by mass, the adhesion to the plastic substrate may be lowered, and when the chlorine content is less than 10%, the solution stability may be lowered, which is not preferable.
The amount of the acid anhydride to be introduced into the chlorinated polyolefin (d) having an acid anhydride group is preferably 0.1 to 8 parts by mass, more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the chlorinated polyolefin (d) having an acid anhydride group. When the amount of the acid anhydride to be incorporated is less than 0.1 part by mass, the interlayer adhesion in the case of using the composition for a multilayer coating film may be low, and when it exceeds 8 parts by mass, the adhesion to a plastic substrate may be low.
When the chlorinated polyolefin (d) having an acid anhydride group is reacted with a compound having an allyloxy group and a hydroxyl group, the compound having an allyloxy group and a hydroxyl group is added to the acid anhydride group to obtain the chlorinated polyolefin (b) having an allyloxy group. As the compound having an allyloxy group and a hydroxyl group, for example, the compound (a) having an allyloxy group and a hydroxyl group represented by the above general formula (I) can be used.
The amount of the compound having an allyloxy group and a hydroxyl group used in the reaction with the chlorinated polyolefin (d) having an acid anhydride group is preferably in the range of 0.2 to 300 mol, and more preferably in the range of 0.5 to 150 mol, based on 1 mol of the acid anhydride group. When the amount of the compound having an allyloxy group and a hydroxyl group is less than 0.2 mol, curability of the polymer composition containing the modified chlorinated polyolefin may be low, and when it exceeds 300 mol, the amount of the unreacted compound having an allyloxy group and a hydroxyl group remaining in a part after copolymerization may be too large, and stability of the polymer composition containing the modified chlorinated polyolefin may be low.
The reaction of the chlorinated polyolefin (d) having an acid anhydride group with the compound having an allyloxy group and a hydroxyl group is not particularly limited, and can be carried out according to a conventional method of reacting an acid anhydride group with a hydroxyl group. Specifically, for example, the reaction can be carried out by heating the chlorinated polyolefin (d) having an acid anhydride group and a compound having an allyloxy group and a hydroxyl group at about 20 to about 160 ℃, preferably about 60 to about 120 ℃, more preferably about 80 to about 110 ℃ for about 0.5 to about 72 hours. In order to increase the degree of progress of the reaction, the reaction may be carried out at a high temperature and then maintained at a low temperature.
In the above reaction, a catalyst for promoting the reaction may be used. Examples of the catalyst include dibutyltin oxide, dibutyltin dilaurate, antimony trioxide, zinc acetate, and ethyl acetateLewis acidic metal compounds such as manganese acid, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate and tetraisopropyl titanate; tetrabutylammonium bromide and tetraphenylphosphonium chloride
Figure BDA0002173612280000061
Etc. of
Figure BDA0002173612280000062
Salts; basic nitrogen-containing compounds such as triethylamine and triazole, and the like.
In addition, a polymerization inhibitor may be used in the above reaction. Examples of the polymerization inhibitor include compounds containing a phenolic hydroxyl group such as di-t-butylhydroxytoluene and methoxyphenol; carbonyl group-containing aromatic compounds such as benzoquinone; compounds containing a nitroso skeleton; n-oxyl skeleton-containing compounds and the like are known per se as polymerization inhibitors.
In addition, when the chlorinated polyolefin (b) having an allyloxy group is obtained by addition reaction of the chlorinated polyolefin (d) having an acid anhydride group and the compound (a) having an allyloxy group and a hydroxyl group represented by the above general formula (I), a hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group may be added as necessary in addition to the compound (a) having an allyloxy group and a hydroxyl group. Examples of the hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group include alcohols and compounds having a (meth) acryloyl group and a hydroxyl group.
Examples of such alcohols include: alkanols such as methanol, ethanol, propanol, butanol, and 2-ethylhexanol; ether group-containing alcohols such as ethylene glycol monobutyl ether, propylene glycol monopropyl ether, and diethylene glycol monomethyl ether; aromatic alcohols such as benzyl alcohol; carbonyl group-containing alcohols such as diacetone alcohol; and polyhydric alcohols such as diethylene glycol, tripropylene glycol, 1, 6-hexanediol, and trimethylolpropane.
Examples of the compound having a (meth) acryloyl group and a hydroxyl group include monoesters of (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; and modified epsilon-caprolactone of monoester of (meth) acrylic acid and C2-C8 dihydric alcohol.
In addition, in the case where the compound (a) having an allyloxy group and a hydroxyl group represented by the above general formula (I) and a hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group are added to the chlorinated polyolefin (d) having an acid anhydride group, the chlorinated polyolefin (d) having an acid anhydride group may be subjected to an addition reaction with the compound (a) having an allyloxy group and a hydroxyl group, and then subjected to an addition reaction with a hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group; the chlorinated polyolefin (d) having an acid anhydride group may be added with a preliminary mixture of the compound (a) having an allyloxy group and a hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group to cause an addition reaction, or the chlorinated polyolefin (d) having an acid anhydride group may be reacted with a hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group and then subjected to an addition reaction with the compound (a) having an allyloxy group and a hydroxyl group. When a hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group is further added to the chlorinated polyolefin (d) having an acid anhydride group, the amount of the hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group to be used is not particularly limited, and is preferably 500 moles or less, more preferably 300 moles or less, based on 1 mole of the acid anhydride group of the chlorinated polyolefin (d) having an acid anhydride group. When the amount is more than 500 moles, the stability of the polymer composition containing the modified chlorinated polyolefin is sometimes low. When the hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group contains a compound having a (meth) acryloyl group and a hydroxyl group, the amount of the compound having a (meth) acryloyl group and a hydroxyl group to be used is preferably 10 moles or less, more preferably 5 moles or less, based on 1 mole of the acid anhydride group of the chlorinated polyolefin (d) having an acid anhydride group. When the amount is more than 10 mol, the system may be easily gelled in the copolymerization step.
[ polymerizable monomer containing 1 or more compounds (c) selected from (meth) acrylate, (meth) acrylic acid and styrene ]
In the present specification, "(meth) acrylic acid" means "acrylic acid or methacrylic acid", "(meth) acrylate" means "acrylate or methacrylate", "(meth) acryloyl" means "acryloyl or methacryloyl", and "(meth) acrylate" means "acrylate or methacrylate". The (meth) acrylate used in the present invention is not particularly limited, and examples thereof include: alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, and isophorone (meth) acrylate; hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; di (meth) acrylates such as ethylene glycol di (meth) acrylate; allyl group-containing (meth) acrylates such as allyl (meth) acrylate; epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate; phosphoric acid group-containing (meth) acrylates such as 2- ((meth) acryloyloxy) ethyl phosphate, acidic phospho (phospho) polyoxyethylene glycol mono (meth) acrylate, and acidic phospho polyoxypropylene glycol mono (meth) acrylate. Further, styrene may be substituted, and in this case, alkyl-substituted styrenes such as methylstyrene and ethylstyrene are exemplified. These polymerizable monomers may be used alone or in combination of 2 or more, respectively, for adjusting the molecular weight, hardness, polarity, adhesiveness, solution viscosity, solution stability, compatibility, and the like of the polymer composition.
[ copolymerization of a chlorinated polyolefin (b) having an allyloxy group and a polymerizable monomer containing a compound (c) in the coexistence of the compound (a) ]
In the present invention, a modified chlorinated polyolefin is produced by copolymerizing a chlorinated polyolefin (b) having an allyloxy group and a polymerizable monomer containing at least 1 compound (c) selected from the group consisting of a (meth) acrylate, a (meth) acrylic acid and styrene in the coexistence of a compound (a) having an allyloxy group and a hydroxyl group. The amount of each of the compound (a), the chlorinated polyolefin (b) having an allyloxy group, and the polymerizable monomer containing 1 or more compounds (c) selected from the group consisting of (meth) acrylate, (meth) acrylic acid, and styrene used in the copolymerization is preferably in the following range based on 100 parts by mass of the total solid content of the above components (a) to (c).
The amount of the compound (a) having an allyloxy group and a hydroxyl group is 0.05 to 40 parts by mass, preferably 0.1 to 30 parts by mass, and more preferably 0.2 to 20 parts by mass.
The amount of the chlorinated polyolefin (b) having an allyloxy group is 1 to 89.95 parts by mass, preferably 5 to 60 parts by mass, and more preferably 10 to 35 parts by mass.
10 to 98.95 parts by mass, preferably 35 to 95 parts by mass, and more preferably 65 to 90 parts by mass of 1 or more compounds (c) selected from the group consisting of (meth) acrylate, (meth) acrylic acid, and styrene.
In the present invention, when the chlorinated polyolefin (b) having an allyloxy group and the polymerizable monomer containing the compound (c) of 1 or more selected from the group consisting of (meth) acrylate, (meth) acrylic acid and styrene are copolymerized in the coexistence of the compound (a) having an allyloxy group and a hydroxyl group, a copolymerization component other than the (meth) acrylate, (meth) acrylic acid and styrene can be further added. Examples of such other copolymerizable components include aliphatic carboxylic acid vinyl esters such as vinyl acetate, vinyl octanoate, and vinyl decanoate. In addition, in order to adjust the molecular weight, liquid stability, compatibility and the like of the polymer composition, copolymerization may be carried out in the presence of 1 or more species selected from chlorinated polyolefins having no allyloxy group and chlorinated polyolefins having no acid anhydride group.
In the present invention, when copolymerizing a chlorinated polyolefin (b) having an allyloxy group (hereinafter, sometimes simply referred to as "(b)") and a polymerizable monomer (hereinafter, sometimes simply referred to as "(c)") containing at least 1 compound (c) selected from the group consisting of a (meth) acrylate, a (meth) acrylic acid and styrene in the presence of a compound (a) having an allyloxy group and a hydroxyl group (hereinafter, sometimes simply referred to as "(a)"), any of the following methods can be used in order to adjust the molecular weight, liquid stability, compatibility and the like of the polymer composition: (ii) adding (b) to the reaction vessel in advance, and then polymerizing while adding (c); (ii) adding (b) to the reaction vessel in advance, and then polymerizing while adding (b) and (c); adding (b) and (c) to a reaction tank, and then polymerizing together; adding (b) and (c) to a reaction tank in advance, and then polymerizing while adding (b); adding (b) and (c) to a reaction vessel in advance, and then polymerizing while adding a polymerizable monomer containing the compound (c); adding (b) and (c) to a reaction tank in advance, and then polymerizing while adding (b) and (c); polymerizing while adding (b) and (c) to the reaction vessel; (ii) adding (c) to the reaction vessel in advance, and then polymerizing while adding (b); (ii) adding (c) to the reaction vessel in advance, and then polymerizing while adding (b) and (c); and the like. In addition, the polymerization step may be divided into a plurality of stages, and these methods may be used in combination. For example, combinations of: a step of adding (b) and (c) to the reaction tank in the 1 st stage and then polymerizing them together, and a step of adding (b) and/or (c) to the reaction tank in the 2 nd stage and polymerizing them together; or may be used in combination: a step of polymerizing while adding (b) and (c) to the reaction tank in the 1 st stage, and a step of polymerizing while adding (b) and/or (c) to the reaction tank in the 2 nd stage. In addition, in the case where the polymerization step is divided into a plurality of stages, the respective compositions of (b) and/or (c) used in the respective steps may be the same or different.
In addition, in the case where the chlorinated polyolefin (d) having an acid anhydride group and the compound (a) having an allyloxy group and a hydroxyl group are mixed and subjected to an addition reaction to obtain the chlorinated polyolefin (b) having an allyloxy group, a mixture in which the chlorinated polyolefin (b) having an allyloxy group and the unreacted compound (a) having an allyloxy group and a hydroxyl group coexist can be obtained by not completing the addition reaction or by making the number of moles of the compound (a) having an allyloxy group and a hydroxyl group mixed larger than the number of moles of the acid anhydride group. In this case, by copolymerizing the mixture with the polymerizable monomer containing the compound (c), the chlorinated polyolefin (b) having an allyloxy group and the polymerizable monomer containing the compound (c) selected from 1 or more of (meth) acrylate, (meth) acrylic acid and styrene can be copolymerized in the coexistence of the compound (a) having an allyloxy group and a hydroxyl group. In the copolymerization of the chlorinated polyolefin (b) having an allyloxy group and the polymerizable monomer containing the compound (c), the chlorinated polyolefin (b) having an allyloxy group and the compound (a) having an allyloxy group and a hydroxyl group are mixed in advance, or the polymerizable monomer containing the compound (c) and the compound (a) having an allyloxy group and a hydroxyl group are mixed in advance, whereby the chlorinated polyolefin (b) having an allyloxy group and the polymerizable monomer containing the compound (c) selected from the group consisting of (meth) acrylate, (meth) acrylic acid and styrene can be copolymerized in the coexistence of the compound (a) having an allyloxy group and a hydroxyl group.
In the present invention, the method of copolymerizing the chlorinated polyolefin (b) having an allyloxy group and the polymerizable monomer containing the 1 or more compounds (c) selected from the group consisting of (meth) acrylate, (meth) acrylic acid and styrene in the coexistence of the compound (a) having an allyloxy group and a hydroxyl group is not particularly limited, and a known copolymerization method can be used, and among them, a solution polymerization method of polymerizing in an organic solvent in the presence of a polymerization initiator can be suitably used.
Examples of the organic solvent used in the solution polymerization method include aromatic solvents such as toluene, xylene, "スワゾール 1000" (product name, high-boiling point petroleum solvent, manufactured by コスモ petroselm corporation); alicyclic solvents such as cyclohexane and methylcyclohexane; aliphatic solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, 3-methoxybutyl acetate, butyl propionate, ethyl 3-ethoxypropionate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; alcohol solvents such as butanol, 2-ethylhexanol, ethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether. These may be used in combination of 2 or more.
The amount of the organic solvent used in the polymerization reaction is not particularly limited, and may be suitably adjusted to adjust the stability of the polymer composition containing the modified chlorinated polyolefin, and the like. From the viewpoint of improving the production efficiency, it is usually preferably in the range of 500 parts by mass or less, preferably 50 to 400 parts by mass, and more preferably 100 to 300 parts by mass, based on 100 parts by mass of the total solid content of the components (a) to (c).
The organic solvent may be added after the copolymerization reaction. Further, the copolymerization reaction may be followed by solvent removal.
As the polymerization initiator, known compounds can be used, and examples thereof include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; peroxy ketals such as di (t-hexylperoxy) cyclohexane and di (t-butylperoxy) cyclohexane; hydrogen peroxides such as p-menthane hydrogen peroxide; dialkyl peroxides such as di-t-butyl peroxide, di (2-t-butylperoxyisopropyl) benzene, and dicumyl peroxide; diacyl peroxides such as diisobutyryl peroxide, bis (3,5, 5-trimethylhexanoyl) peroxide, and dilauroyl peroxide; peroxydicarbonates such as di (2-ethylhexyl) peroxydicarbonate, diisopropyl peroxydicarbonate and di (4-tert-butylcyclohexyl) peroxydicarbonate; peroxycarbonates such as t-butyl peroxyisopropyl carbonate and 2-ethylhexyl tert-butyl peroxycarbonate; peroxy esters such as t-butyl peroxypivalate, t-butyl peroxylaurate, t-butyl peroxy2-ethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, 2, 5-dimethyl-2, 5-di (2-ethylhexanoylperoxy) hexane, and di-t-butyl peroxyhexahydroterephthalate; azo compounds such as azobisisobutyronitrile, azobis (2, 4-dimethylvaleronitrile), azobis (2-methylpropanenitrile), azobis (2-methylbutyronitrile), 4' -azobis (4-cyanovaleric acid), dimethyl azobis (2-methylpropaneate), azobis [ 2-methyl-N- (2-hydroxyethyl) -propionamide ], azobis { 2-methyl-N- [2- (1-hydroxybutyl) ] -propionamide }; persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate. The polymerization initiator may be a monofunctional type or a polyfunctional type depending on the radical generated.
These polymerization initiators may be used alone or in combination of 2 or more. In addition, a reducing agent such as sugar, sodium formaldehyde sulfoxylate, or an iron complex may be used as a redox initiator in combination as necessary in the above-mentioned polymerization initiator.
The amount of the polymerization initiator used is preferably in the range of usually 0.1 to 10 parts by mass, preferably 0.5 to 8 parts by mass, and more preferably 1 to 6 parts by mass, based on 100 parts by mass of the total solid content of the components (a) to (c). The molecular weight of the polymer composition containing the modified chlorinated polyolefin can be changed by changing the amount of the polymerization initiator used. The molecular weight is preferably from about 30,000 to about 400,000, more preferably from about 70,000 to about 200,000, for ease of manufacture at a weight average molecular weight of from about 10,000 to about 1,000,000, to improve solution stability and compatibility of the polymer composition, and the like.
In the present specification, the weight average molecular weight is a value obtained by converting the retention time (retention capacity) of a standard polystyrene having a known molecular weight, which is measured under the same conditions, into the molecular weight of the polystyrene, using the retention time (retention capacity) measured by a Gel Permeation Chromatograph (GPC). Specifically, the measurement can be performed under the following conditions: as a gel permeation chromatography apparatus, "HLC-8120 GPC" (trade name, manufactured by eastern cao corporation) was used, as a column, 4 columns of "TSKgel G4000 HXL", "TSKgel G3000 HXL", "TSKgel G2500 HXL", and "TSKgel G2000 HXL" (trade name, manufactured by eastern cao corporation) were used, as a detector, a differential refractometer was used, and a mobile phase: tetrahydrofuran, measurement temperature: 40 ℃, flow rate: 1 mL/min.
The method of adding the polymerization initiator is not particularly limited, and may be appropriately selected depending on the kind and amount thereof. For example, it may be contained in the monomer mixture or the solvent in advance, or may be added together or dropped at the time of polymerization.
The copolymerization reaction can be carried out usually at 20 to 170 ℃, preferably 70 to 130 ℃, and more preferably 80 to 120 ℃.
Further, an antioxidant may be added after the above copolymerization reaction. Examples of the antioxidant include compounds containing a phenolic hydroxyl group such as di-t-butylhydroxytoluene and methoxyphenol; and aromatic compounds containing a carbonyl group such as benzoquinone.
[ Polymer composition containing modified chlorinated polyolefin ]
The polymer composition containing a modified chlorinated polyolefin of the present invention may contain a crosslinking agent as needed. As the crosslinking agent, any crosslinking agent may be used as long as it can be combined with the polymer composition containing the modified chlorinated polyolefin to prepare a curable composition, but in general, a crosslinking agent reactive with hydroxyl groups contained in the modified chlorinated polyolefin or the like is suitably used. As such a crosslinking agent having reactivity with a hydroxyl group, for example, a polyisocyanate compound, a blocked polyisocyanate compound, an amino resin, or the like can be suitably used. The crosslinking agents may be used singly or in combination of 2 or more.
The polyisocyanate compound is a compound having at least 2 isocyanate groups in 1 molecule, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.
Examples of the aliphatic polyisocyanate include aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propane diisocyanate, 1, 2-butane diisocyanate, 2, 3-butane diisocyanate, 1, 3-butane diisocyanate, 2,4, 4-or 2,2, 4-trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, and methyl 2, 6-diisocyanatohexanoate (common name: lysine diisocyanate); aliphatic triisocyanates such as 2-isocyanatoethyl 2, 6-diisocyanatohexanoate, 1, 6-diisocyanato-3-isocyanatomethylhexane, 1,4, 8-triisocyanatooctane, 1,6, 11-triisocyanatoundecane, 1, 8-diisocyanato-4-isocyanatomethyloctane, 1,3, 6-triisocyanatohexane and 2,5, 7-trimethyl-1, 8-diisocyanato-5-isocyanatomethyloctane.
Examples of the alicyclic polyisocyanate include 1, 3-cyclopentene diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), 4-methyl-1, 3-cyclohexene diisocyanate (common name: hydrogenated TDI), alicyclic diisocyanates such as 2-methyl-1, 3-cyclohexene diisocyanate, 1, 3-or 1, 4-bis (isocyanatomethyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, methylenebis (4, 1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), norbornane diisocyanate and the like; 1,3, 5-triisocyanatocyclohexane, 1,3, 5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2, 5-bis (isocyanatomethyl) -bicyclo (2.2.1) heptane, 2- (3-isocyanatopropyl) -2, 6-bis (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2, 5-bis (isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane Alicyclic triisocyanates such as propyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) -heptane, and 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane.
Examples of the aromatic aliphatic polyisocyanate include aromatic aliphatic diisocyanates such as methylenebis (4, 1-phenylene) diisocyanate (common name: MDI), 1, 3-or 1, 4-xylylene diisocyanate or a mixture thereof, ω' -diisocyanato-1, 4-diethylbenzene, 1, 3-or 1, 4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof; aromatic aliphatic triisocyanates such as 1,3, 5-triisocyanatomethylbenzene, and the like.
Examples of the aromatic polyisocyanate include aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, 2, 4-toluene diisocyanate (common name: 2,4-TDI), 2, 6-toluene diisocyanate (common name: 2,6-TDI), or a mixture thereof, 4' -toluidine diisocyanate, 4' -diphenyl ether diisocyanate, and the like; aromatic triisocyanates such as triphenylmethane-4, 4', 4 ″ -triisocyanate, 1,3, 5-triisocyanatobenzene, 2,4, 6-triisocyanatotoluene and the like; and aromatic tetraisocyanates such as 4,4' -diphenylmethane-2, 2 ', 5,5 ' -tetraisocyanate.
Further, as the derivatives of the above-mentioned polyisocyanate, there may be mentioned, for example, dimers, trimers, biurets, allophanates, uretdiones, uretonimines, isocyanurates, uretonimines, uretdiones, uretonimines, and the compounds of the above-substituted or the compounds of the above-substituted or the formula (I, and the compounds of the formula (I, and the above-substituted or (II, and (II) may be mentioned as,
Figure BDA0002173612280000141
Diazinetrione (oxazinetrione), polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI), crude TDI, and the like.
The above polyisocyanates and derivatives thereof may be used singly or in combination of 2 or more. In addition, among these polyisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and their derivatives are preferable.
As the polyisocyanate compound, a prepolymer obtained by reacting the polyisocyanate and its derivative with a compound reactive with the polyisocyanate under a condition of excess isocyanate groups can be used. Examples of the compound reactive with the polyisocyanate include compounds having an active hydrogen group such as a hydroxyl group or an amino group, and specific examples thereof include polyols, low molecular weight polyester resins, amines, and water.
The polyisocyanate compound may be a polymer of an isocyanate group-containing polymerizable unsaturated monomer or a copolymer of the isocyanate group-containing polymerizable unsaturated monomer and a polymerizable unsaturated monomer other than the isocyanate group-containing polymerizable unsaturated monomer.
The equivalent ratio (NCO/OH) of the isocyanate group in the polyisocyanate compound to the hydroxyl group in the resin component in the polymer composition containing a modified chlorinated polyolefin is preferably a ratio in the range of usually 0.5 to 2.5, particularly preferably 0.8 to 1.9, from the viewpoint of curability and the like.
The blocked polyisocyanate compound is a compound obtained by blocking the isocyanate group of the polyisocyanate compound with a blocking agent.
Examples of the blocking agent include phenol-based compounds such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and methyl hydroxybenzoate; lactam systems such as epsilon-caprolactam, delta-valerolactam, gamma-butyrolactam and beta-propiolactam; aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, and lauryl alcohol; ether systems such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and methoxymethanol; alcohol systems such as benzyl alcohol, glycolic acid, methyl glycolate, ethyl glycolate, butyl glycolate, lactic acid, methyl lactate, ethyl lactate, butyl lactate, methylol urea, methylol melamine, diacetone alcohol, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate; oxime systems such as formamide oxime, acetamide oxime, acetone oxime, methyl ethyl ketone oxime, diacetyl monooxime, benzophenone oxime, and cyclohexane oxime; malonic acid diester esters having an active methylene position such as dimethyl malonate, diethyl malonate, ethylmethyl malonate, bis (2-methoxy-1-methylethyl) malonate, and acetyl group-containing compounds having an active methylene position such as ethyl acetoacetate, methyl acetoacetate, and acetylacetone; mercaptan systems such as butanethiol, tert-butylmercaptan, hexanethiol, tert-dodecylmercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol, and ethylthiophenol; amide systems such as acetanilide, methoxyacetanilide, acetyltoluidine, acrylamide, methacrylamide, acetamide, stearamide, and benzamide; imide-based compounds such as succinimide, phthalimide and maleimide; amine systems such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine, and butylaniline; imidazole systems such as imidazole and 2-ethylimidazole; urea systems such as urea, thiourea, ethylene urea, ethylene thiourea and diphenylurea; carbamates such as phenyl N-phenylcarbamate; imine systems such as ethyleneimine and propyleneimine; sulfite-based compounds such as sodium hydrogen sulfite and potassium hydrogen sulfite; azole compounds, and the like. Examples of the azole compound include pyrazole or pyrazole derivatives such as pyrazole, 3, 5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3, 5-dimethylpyrazole, 4-nitro-3, 5-dimethylpyrazole, 4-bromo-3, 5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole; imidazole or imidazole derivatives such as imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole and 2-phenylimidazole; imidazoline derivatives such as 2-methylimidazoline and 2-phenylimidazoline, and the like.
Among them, preferable examples of the blocking agent include oxime-based blocking agents, malonic acid diester-based or acetyl group-containing compound-based blocking agents having an active methylene position, and pyrazole or pyrazole derivatives.
When the capping reaction (the reaction of the capping agent) is carried out, a solvent may be added as needed. The solvent used in the blocking reaction is preferably a solvent that is not reactive with isocyanate groups, and examples thereof include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and solvents such as N-methyl-2-pyrrolidone (NMP).
When the polyisocyanate compound and/or the blocked polyisocyanate compound are used as the crosslinking agent, a catalyst for a conventional urethanization reaction can be used as the catalyst. Examples of the catalyst include organic metal compounds such as tin octylate, dibutyltin diacetate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, dioctyltin bis (2-ethylhexanoate), dibutyltin oxide, dibutyltin sulfite, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, zinc fatty acid, bismuth octylate, bismuth 2-ethylhexanoate, bismuth oleate, bismuth neodecanoate, bismuth versatate, bismuth naphthenate, cobalt naphthenate, calcium octylate, copper naphthenate, and tetrakis (2-ethylhexyl) titanate; tertiary amines and the like, and they may be used alone or in combination of 2 or more.
When a catalyst is used, the amount of the catalyst is preferably in the range of 0.0001 to 1% by mass, and particularly preferably in the range of 0.0005 to 0.5% by mass, based on the total amount of solid components in the polymer composition.
When the polymer composition contains the catalyst, the polymer composition may contain the following from the viewpoint of storage stability, curability, and the like: organic acids such as acetic acid, propionic acid, butyric acid, isovaleric acid, caproic acid, 2-ethylbutyric acid, naphthenic acid, caprylic acid, pelargonic acid, capric acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, tertiary carboxylic acid, isobutyric anhydride, itaconic anhydride, acetic anhydride, citraconic anhydride, propionic anhydride, maleic anhydride, butyric anhydride, citric anhydride, trimellitic anhydride, pyromellitic anhydride, and phthalic anhydride; inorganic acids such as hydrochloric acid and phosphoric acid; metal-coordinating compounds such as acetylacetone and imidazole compounds.
As the amino resin, a partially methylolated amino resin or a completely methylolated amino resin obtained by reacting an amino component with an aldehyde component can be used. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, stereoguanamine (steroguanamine), spiroguanamine (spiroguanamine), and dicyandiamide. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.
Further, an amino resin in which methylol groups of the above methylolated amino resin are partially or completely etherified with an appropriate alcohol may be used. Examples of the alcohol used for etherification include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylbutanol, and 2-ethylhexanol.
As the amino resin, a melamine resin is preferable. As the melamine resin, for example, an alkyl etherified melamine resin in which methylol groups of a partially or completely methylolated melamine resin are partially or completely etherified with the above-mentioned alcohol can be used.
As the above-mentioned alkyl-etherified melamine resin, for example, there can be suitably used: a methyl-etherified melamine resin in which methylol groups of a partially or fully methylolated melamine resin are partially or fully etherified with methanol; a butyl-etherified melamine resin in which methylol groups of a partially or fully methylolated melamine resin are partially or fully etherified with butanol; and a methyl-butyl mixed etherified melamine resin in which methylol groups of a partially or completely methylolated melamine resin are partially or completely etherified with methanol and butanol.
As the melamine resin, commercially available products can be used. Examples of the trade names of commercially available products include "サイメル 202", "サイメル 203", "サイメル 238", "サイメル 251", "サイメル 303", "サイメル 323", "サイメル 324", "サイメル 325", "サイメル 327", "サイメル 350", "サイメル 385", "サイメル 1156", "サイメル 1158", "サイメル 1116" and "サイメル 1130" (see above, manufactured by オルネクス japan), "ユーバン 120", "ユーバン 20 HS", "ユーバン 20SE 60", "ユーバン 2021 SE 1", "ユーバン 2028" and "ユーバン 28-60" (see above, manufactured by mitsui chemical).
The melamine resins mentioned above may be used singly or in combination of 2 or more.
In addition, as the crosslinking agent, in the case of using melamine resin, can use toluene sulfonic acid, dodecylbenzene sulfonic acid, two nonyl naphthalene sulfonic acid and other sulfonic acid; alkyl phosphates such as monobutyl phosphate, dibutyl phosphate, mono (2-ethylhexyl) phosphate, di (2-ethylhexyl) phosphate; salts of these acids with amine compounds, and the like are used as catalysts.
The polymer composition containing a modified chlorinated polyolefin of the present invention, which is obtained by copolymerizing a chlorinated polyolefin (b) having an allyloxy group and a polymerizable monomer containing at least 1 compound (c) selected from the group consisting of a (meth) acrylate, a (meth) acrylic acid and styrene in the presence of a compound (a) having an allyloxy group and a hydroxyl group, is suitably used as a curable composition and a coating composition. When the polymer composition containing a modified chlorinated polyolefin of the present invention is used as a coating composition, it preferably contains the above-mentioned crosslinking agent reactive with hydroxyl groups. The coating composition may contain, as required, various additives used in the field of coating materials, such as coating resins including epoxy resins, acrylic resins, polyester resins, urethane resins, chlorinated polyolefins, various pigments, viscosity modifiers, pigment dispersants, defoaming agents, and ultraviolet absorbers.
The coating composition of the present invention can be applied using various known coating methods. The object to be coated is not particularly limited, and can be applied to, for example, a molded article, a plastic substrate such as a film, or the like.
Examples
The present invention will be described in more detail below with reference to production examples, examples and comparative examples. However, the present invention is not limited thereto. In each example, "part(s)" and "%" are based on mass unless otherwise specified. The film thickness of the coating film is based on the film thickness of the cured coating film.
Production of Polymer compositions containing modified chlorinated polyolefins
Example 1
100 parts of "スーパークロン 822S" (trade name, maleic anhydride-modified chlorinated polyolefin, manufactured by Nippon paper-making Co., Ltd., chlorine content: 24.5%), 221 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT) were charged into a four-necked flask equipped with a cooling tube, and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. To this, 57.5 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was decreased to about 90 ℃ to obtain a solution containing about 55 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. Then, 197 parts of methyl methacrylate and 197 parts of cyclohexyl methacrylate were added dropwise over about 4 hours as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid esters, (meth) acrylic acid and styrene, while stopping blowing of air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase189 parts of ester, 10 parts of styrene, 2 parts of acrylic acid, 2 parts of ethylene glycol dimethacrylate and 5 parts (3.5 parts of active ingredient) of Perbutyl PV (a 70% hydrocarbon solution of t-butyl peroxypivalate, manufactured by Nichiol corporation) 189.5 parts of toluene and 63 parts of butyl acetate, and a mixed solution of 5 parts (3.5 parts of active ingredient) of Perbutyl PV and 70 parts of toluene was added dropwise thereto over about 1 hour, followed by stirring for about 1 hour and cooling to room temperature to obtain a polymer composition (P-1) containing a modified chlorinated polyolefin. The resulting polymer composition (P-1) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 45 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 11 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 2
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S" (trade name, maleic anhydride-modified chlorinated polyolefin, manufactured by Japan paper-making Co., Ltd., chlorine content: 24.5%), 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. To this mixture were added 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide, and stirring was continued while reacting the 2-allyloxyethanol with an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was reduced to about 90 ℃ while keeping the absorbance ratio of (a) above, and 150 parts of toluene and 34.5 parts of 2-allyloxyethanol were further added to the reaction solution, thereby obtaining a solution containing about 55 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group, and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. Then, 197 parts of methyl methacrylate, 191 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid, and Per were added dropwise over about 4 hours as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid ester, (meth) acrylic acid, and styrene, while stopping blowing of air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase5 parts of butyl PV, 189.5 parts of toluene and 63 parts of butyl acetate, and further 1 hour after which 5 parts of Perbutyl PV and 70 parts of toluene were added dropwise thereto, followed by stirring for about 1 hour and cooling to room temperature to obtain a polymer composition (P-2) containing a modified chlorinated polyolefin. The resulting polymer composition (P-2) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 45 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 11 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 3
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 3228S" (trade name, maleic anhydride-modified chlorinated polyolefin, manufactured by Japan paper-making Co., Ltd., chlorine content: 28%), 210 parts of toluene, 11 parts of butyl acetate, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. To this, 57.5 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was decreased to about 90 ℃ to obtain a solution containing about 55 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid ester, (meth) acrylic acid and styrene, a mixture of 205 parts of methyl methacrylate, 183 parts of cyclohexyl methacrylate, 8 parts of methacrylic acid, 4 parts of ethylene glycol dimethacrylate, 5 parts of Perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate was added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, continuing stirring for about 1 hour, and then cooling to room temperature to obtain a polymerized product containing the modified chlorinated polyolefinComposition (P-3). The resulting polymer composition (P-3) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 45 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 11 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 4
A four-necked flask equipped with a cooling tube was charged with 50 parts of "ハードレン F-6P" (trade name, manufactured by Toyo Boseki Co., Ltd., chlorinated polyolefin modified with maleic anhydride, chlorine content: 20%), 214 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. To this, 65 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was decreased to about 90 ℃ to obtain a solution containing about 64 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group and having a concentration of about 16% of chlorinated polyolefin (b) having an allyloxy group. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylate, (meth) acrylic acid and styrene, a mixture of 214 parts of methyl methacrylate, 222 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid, 2 parts of ethylene glycol dimethacrylate, 5 parts of Perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate was added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise again over about 1 hour, continuing stirring for about 1 hour, and then cooling to room temperature, thereby obtaining a polymer composition (P-4) containing a modified chlorinated polyolefin. The resulting polymer composition (P-4) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 52 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 12 mgKOH/g. In addition, chlorinated polyalkenes in the compositionThe composition ratio of the hydrocarbon skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol was about 10/90.
Example 5
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 221 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and heated to about 95 ℃ to prepare a solution. To this solution, 82.5 parts of diethylene glycol monoallyl ether and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting the diethylene glycol monoallyl ether with an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1And the temperature was decreased to about 90 ℃ to obtain a solution containing about 79 parts of diethylene glycol monoallyl ether which is the compound (a) having an allyloxy group and a hydroxyl group, and having a concentration of about 25% of the chlorinated polyolefin (b) having an allyloxy group. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylate, (meth) acrylic acid and styrene, 187 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 20 parts of styrene, 2 parts of acrylic acid, 2 parts of ethylene glycol dimethacrylate, and a mixture of 5 parts of Perbutyl PV, 189.5 parts of toluene and 39 parts of butyl acetate was added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise again over about 1 hour, continuing stirring for about 1 hour, and then cooling to room temperature, thereby obtaining a polymer composition (P-5) containing a modified chlorinated polyolefin. The resulting polymer composition (P-5) containing a modified chlorinated polyolefin had a solid content of about 47% and contained about 65 parts of diethylene glycol monoallyl ether in the composition. The hydroxyl value of the solid resin component was about 15 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to an acrylic resin skeleton obtained by copolymerizing a part of diethylene glycol monoallyl ether of about 19/81.
Example 6
A four-necked flask with a cooling tube was charged with 100 parts of "スーパークロン 822S", 228 parts of toluene and di-t-butyl hydroxy0.05 part of toluene (BHT) was added to the liquid phase, and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. To this, 46 parts of 2-allyloxyethanol, 4 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol, butanol and an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was decreased to about 90 ℃ to obtain a solution containing about 44 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. The approximate molar ratio of 2-allyloxyethanol reacted with the acid anhydride group to butanol was 0.8/0.2. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylate, (meth) acrylic acid and styrene, a mixture of 197 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid, 2 parts of ethylene glycol dimethacrylate, 5 parts of Perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate was added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise again over about 1 hour, continuing stirring for about 1 hour, and then cooling to room temperature, thereby obtaining a polymer composition (P-6) containing a modified chlorinated polyolefin. The resulting polymer composition (P-6) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 36 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 9 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 7
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and heated to about 95 ℃ to prepare a solution. To this, 11.5 parts of 2-allyloxyethanol, 17 parts of butanol and 0.1 part of tetrabutylammonium bromide were added while reacting 2-allylThe oxyethanol, butanol and the acid anhydride group were reacted while continuing the stirring. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was lowered to about 90 ℃ while the absorbance ratio of (a) was not substantially changed, and 140 parts of toluene and 39 parts of 2-allyloxyethanol were further added to obtain a solution containing about 50 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. The approximate molar ratio of 2-allyloxyethanol reacted with the acid anhydride group to butanol was 0.2/0.8. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid ester, (meth) acrylic acid and styrene, a mixture of 206 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 3 parts of methacrylic acid, 2 parts of ethylene glycol dimethacrylate and 5 parts of Perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate was added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour while continuing stirring for about 1 hour, followed by cooling to room temperature to obtain a polymer composition (P-7) containing a modified chlorinated polyolefin. The resulting polymer composition (P-7) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 42 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 10 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 8
A four-necked flask equipped with a cooling tube was charged with 100 parts of スーパークロン 3228S, 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. 11.5 parts of 2-allyloxyethanol, 16 parts of butanol, 1 part of 2-ethylhexanol, and 0.1 part of tetrabutylammonium bromide were added thereto, and stirring was continued while reacting 2-allyloxyethanol, butanol, 2-ethylhexanol, and an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was lowered to about 90 ℃ while the absorbance ratio of (a) was not substantially changed, and 140 parts of toluene and 39 parts of 2-allyloxyethanol were further added to obtain a solution containing about 50 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. The approximate molar ratio of 2-allyloxyethanol reacted with an acid anhydride group to the other alcohols was 0.2/0.8. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylate, (meth) acrylic acid and styrene, a mixture of 206 parts of methyl methacrylate, 180 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid, 2 parts of ethylene glycol dimethacrylate, 5 parts of Perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate was added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise again over about 1 hour, and continuing stirring for about 1 hour, followed by cooling to room temperature, thereby obtaining a polymer composition (P-8) containing a modified chlorinated polyolefin. The resulting polymer composition (P-8) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 41 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 10 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 9
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and heated to about 95 ℃ to prepare a solution. 11.5 parts of 2-allyloxyethanol, 1 part of 4-hydroxybutyl acrylate and 0.1 part of tetrabutylammonium bromide were added thereto, and stirring was continued while reacting the 2-allyloxyethanol, the 4-hydroxybutyl acrylate and the acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1In a stage in which the absorbance ratio of (A) is not substantially changed, and the temperature is lowered to about 9To the mixture was further added 156 parts of toluene and 39 parts of 2-allyloxyethanol at 0 ℃ to obtain a solution containing about 48 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. The approximate molar ratio of 2-allyloxyethanol reacted with the acid anhydride group to 4-hydroxybutyl acrylate was 0.9/0.1. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid esters, (meth) acrylic acid and styrene, 303 parts of methyl methacrylate, 96 parts of cyclohexyl methacrylate, 1 part of acrylic acid, and a mixture of 5 parts of Perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate were added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was further added dropwise over about 1 hour, continuing stirring for about 1 hour, and then cooling to room temperature, thereby obtaining a polymer composition (P-9) containing a modified chlorinated polyolefin. The resulting polymer composition (P-9) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 39 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 10 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 10
A four-necked flask equipped with a cooling tube was charged with 50 parts of "ハードレン F-6P", 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. To this, 1.3 parts of 2-allyloxyethanol, 3 parts of 2-hydroxyethyl methacrylate, 4 parts of butanol, and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol, 2-hydroxyethyl methacrylate, butanol, and an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1Reducing the temperature to about 90 ℃ without substantially changing the absorbance ratio of (a), and further adding 140 parts of toluene and 60 parts of 2-allyloxyethanol to the mixture to obtain a 2-allyloxy group-containing compound (a) having an allyloxy group and a hydroxyl groupAbout 61 parts of an ethanol base, and a concentration of the chlorinated polyolefin (b) having an allyloxy group of about 16%. The approximate molar ratio of 2-allyloxyethanol, 2-hydroxyethyl methacrylate and butanol reacted with the acid anhydride group was 0.1/0.1/0.8. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid esters, (meth) acrylic acid and styrene, 90 parts of methyl methacrylate, 352 parts of cyclohexyl methacrylate, 5 parts of styrene and 3 parts of acrylic acid, and a mixture of 5 parts of Perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate were added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, continuing stirring for about 1 hour, and then cooling to room temperature to obtain a polymer composition (P-10) containing a modified chlorinated polyolefin. The resulting polymer composition (P-10) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 49 parts of 2-allyloxyethanol. The hydroxyl value of the solid resin component was about 14 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 10/90.
Example 11
A four-necked flask equipped with a cooling tube was charged with 100 parts of スーパークロン 3228S, 221 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. To this, 40 parts of 2-allyloxyethanol, 15 parts of butanol, and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol, butanol, and an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was decreased to about 90 ℃ while keeping the absorbance ratio of (a) above substantially unchanged, to obtain a solution containing about 39 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group, and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. The approximate molar ratio of 2-allyloxyethanol reacted with the acid anhydride group to butanol was 0.5/0.5. Then, blowing of air into the liquid phase is stoppedWhile nitrogen gas was flowed into the gas phase, the mixture was stirred at about 90 ℃ to obtain 1 or more compounds (c) selected from the group consisting of (meth) acrylate, (meth) acrylic acid and styrene, and a mixture of 162 parts of methyl methacrylate, 56 parts of n-butyl acrylate, 144 parts of isophorone acrylate, 36 parts of 2-hydroxyethyl acrylate, 2 parts of ethylene glycol dimethacrylate, and 5 parts of Perbutyl PV, 189.5 parts of toluene, 30 parts of butyl acetate and 33 parts of butanol was added dropwise over about 4 hours, and a mixture of Perbutyl PV 5 parts and 70 parts of toluene was added dropwise over about 1 hour to stir for about 1 hour and then cooled to room temperature, thereby obtaining a polymer composition (P-11) containing a modified chlorinated polyolefin. The resulting polymer composition (P-11) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 32 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 42 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 12
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and heated to about 95 ℃ to prepare a solution. To this mixture were added 30 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide, and the mixture was stirred while reacting the 2-allyloxyethanol with an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was reduced to about 90 ℃ without substantially changing the absorbance ratio of (a), and 178 parts of toluene was further added to obtain a solution containing about 28 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group, and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. Then, while stopping blowing air into the liquid phase, the gas phase was continuously stirred at about 90 ℃ while flowing nitrogen gas, and as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic ester, (meth) acrylic acid and styrene, 303 parts of cyclohexyl methacrylate, 84 parts of n-butyl acrylate, acrylic acid and styrene were added dropwise over about 4 hours10 parts of 2-hydroxyethyl ester, 3 parts of methacrylic acid, and a mixture of 5 parts of Perbutyl PV, 189.5 parts of toluene, 45 parts of butyl acetate, and 18 parts of butanol, followed by dropping the mixture of 5 parts of Perbutyl PV and 70 parts of toluene over about 1 hour, continuing to stir for about 1 hour, and then cooling to room temperature, to obtain a polymer composition (P-12) containing a modified chlorinated polyolefin. The resulting polymer composition (P-12) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 23 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 15 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 13
A four-necked flask equipped with a cooling tube was charged with 100 parts of "ハードレン F-6P", 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. 11.5 parts of 2-allyloxyethanol, 3 parts of 2-hydroxyethyl methacrylate, and 0.1 part of tetrabutylammonium bromide were added thereto, and stirring was continued while reacting the 2-allyloxyethanol, 2-hydroxyethyl methacrylate, and an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was reduced to about 90 ℃ without substantially changing the absorbance ratio of (a) and (b), and 193 parts of toluene was further added to obtain a solution containing about 9 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group, and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. The approximate molar ratio of 2-allyloxyethanol reacted with an acid anhydride group to 2-hydroxyethyl methacrylate was 0.9/0.1. Then, while stopping blowing air into the liquid phase, the gas phase was continuously stirred at about 90 ℃ while flowing nitrogen gas, and as 1 or more compounds (c) selected from the group consisting of (meth) acrylic ester, (meth) acrylic acid and styrene, a mixture of 175 parts of methyl methacrylate, 195 parts of cyclohexyl methacrylate, 26 parts of 2-hydroxyethyl methacrylate, 4 parts of acrylic acid, 5 parts of Perbutyl PV, 189.5 parts of toluene, 33 parts of butyl acetate and 30 parts of butanol was added dropwise over about 4 hoursAfter the mixture was mixed, a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, followed by stirring for about 1 hour and cooling to room temperature, whereby a polymer composition (P-13) containing a modified chlorinated polyolefin was obtained. The resulting polymer composition (P-13) containing a modified chlorinated polyolefin had a solid content of about 45% and contained about 8 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 26 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 14
150 parts of "スーパークロン 822S", 105 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT) were charged into a four-necked flask equipped with a cooling tube, and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. To this, 18 parts of 2-allyloxyethanol, 3 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol, butanol and an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was reduced to about 90 ℃ without substantially changing the absorbance ratio of (a), and 255 parts of toluene was further added to obtain a solution containing about 14 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group, and having a concentration of about 29% of chlorinated polyolefin (b) having an allyloxy group. The approximate molar ratio of 2-allyloxyethanol reacted with the acid anhydride group to butanol was 0.7/0.3. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylate, (meth) acrylic acid and styrene, a mixed solution of 250 parts of cyclohexyl methacrylate, 48 parts of isophorone acrylate, 22 parts of 2-hydroxyethyl methacrylate, 30 parts of styrene, 5 parts of Perbutyl PV, 82.5 parts of toluene, 38 parts of butyl acetate and 27 parts of butanol was added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixed solution of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and continuing stirring for about 1 hour, followed by cooling to room temperature, thereby obtaining a polymer composition (P-14) containing a modified chlorinated polyolefin). The resulting polymer composition (P-14) containing a modified chlorinated polyolefin had a solid content of about 45% and contained about 12 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 22 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 30/70.
Example 15
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and heated to about 95 ℃ to prepare a solution. To this mixture were added 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide, and stirring was continued while reacting the 2-allyloxyethanol with an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was reduced to about 90 ℃ while keeping the absorbance ratio of (a) above, and 150 parts of toluene and 34.5 parts of 2-allyloxyethanol were further added to the reaction solution, thereby obtaining a solution containing about 55 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group, and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. Then, 197 parts of methyl methacrylate, 191 parts of cyclohexyl methacrylate, 10 parts of styrene and 2 parts of acrylic acid were added dropwise over about 4 hours as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid ester, (meth) acrylic acid and styrene under stirring at about 90 ℃ while stopping blowing of air into the liquid phase and flowing nitrogen into the gas phase, and 12 parts (active ingredient: 6 parts) of Perhexa25O (trade name, product of Nichikoku corporation, 50% hydrocarbon solution of 2, 5-dimethyl-2, 5-di (2-ethylhexanoylperoxy) hexane), 189.5 parts of toluene, and 63 parts of butyl acetate, and a mixture of Perhexa25O 6 parts and toluene 70 parts was added dropwise thereto over about 1 hour, followed by stirring for about 1 hour, then cooled to room temperature to obtain a polymer composition (P-15) containing a modified chlorinated polyolefin. The resulting polymer composition (P-15) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 45 parts of 2-allyloxyethanol in the composition. The hydroxyl number of the resin solid component is about11 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 16
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and heated to about 95 ℃ to prepare a solution. To this mixture were added 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide, and stirring was continued while reacting the 2-allyloxyethanol with an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was reduced to about 90 ℃ while keeping the absorbance ratio of (a) above, and 150 parts of toluene and 34.5 parts of 2-allyloxyethanol were further added to the reaction solution, thereby obtaining a solution containing about 55 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group, and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid ester, (meth) acrylic acid and styrene, a mixture of 197 parts of methyl methacrylate, 191 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid and 5 parts of V-65 (trade name, manufactured by Wako pure chemical industries, Ltd., azobis (2, 4-dimethylvaleronitrile)), 189.5 parts of toluene and 63 parts of butyl acetate was added dropwise over about 4 hours, a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and the mixture was stirred for about 1 hour and then cooled to room temperature, thereby obtaining a polymer composition (P-16) containing a modified chlorinated polyolefin. The resulting polymer composition (P-16) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 45 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 11 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 17
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 67 parts of toluene, 3 parts of methylcyclohexane, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and heated to about 95 ℃ to prepare a solution. To this mixture were added 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide, and stirring was continued while reacting the 2-allyloxyethanol with an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was reduced to about 90 ℃ while keeping the absorbance ratio of (a) above, and 145 parts of toluene, 5 parts of methylcyclohexane, and 34.5 parts of 2-allyloxyethanol were further added to the reaction solution, thereby obtaining a solution containing about 55 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group, and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid ester, (meth) acrylic acid and styrene, 197 parts of methyl methacrylate, 191 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid and 5 parts of Perbutyl PV, 171.5 parts of toluene, 18 parts of methylcyclohexane and 63 parts of butyl acetate were added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and then a mixture of 5 parts of Perbutyl PV, 63 parts of toluene and 7 parts of methylcyclohexane was added dropwise over about 1 hour, continuing stirring for about 1 hour, and then cooling to room temperature to obtain a polymer composition (P-17) containing a modified chlorinated polyolefin. The resulting polymer composition (P-17) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 45 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 11 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Example 18
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), stirred while blowing air into the liquid phase, and heated to a temperature ofAbout 95 ℃ to make a solution. To this mixture were added 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide, and stirring was continued while reacting the 2-allyloxyethanol with an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was reduced to about 90 ℃ while keeping the absorbance ratio of (a) above, and 150 parts of toluene and 34.5 parts of 2-allyloxyethanol were further added to the reaction solution, thereby obtaining a solution containing about 55 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group, and having a concentration of about 27% of chlorinated polyolefin (b) having an allyloxy group. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid ester, (meth) acrylic acid and styrene, a mixed solution of 197 parts of methyl methacrylate, 191 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid and 5 parts of Perbutyl PV, 171.5 parts of toluene, 9 parts of cyclohexane, 9 parts of methylcyclohexane and 63 parts of butyl acetate was added dropwise over about 4 hours, a mixed solution of 5 parts of Perbutyl PV, 63 parts of toluene, 3 parts of cyclohexane and 4 parts of methylcyclohexane was added dropwise over about 1 hour, and the mixture was stirred for about 1 hour and then cooled to room temperature, thereby obtaining a polymer composition (P-18) containing a modified chlorinated polyolefin. The resulting polymer composition (P-18) containing a modified chlorinated polyolefin had a solid content of about 46% and contained about 45 parts of 2-allyloxyethanol in the composition. The hydroxyl value of the solid resin component was about 11 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol of about 20/80.
Comparative example 1
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 221 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and heated to about 95 ℃ to prepare a solution. 57.5 parts of 2-hydroxyethyl methacrylate and 0.1 part of tetrabutylammonium bromide were added thereto, and stirring was continued while reacting the 2-hydroxyethyl methacrylate with an acid anhydride group. Solid component in solutionIn the infrared absorption analysis of (2), at about 1770cm-1Absorbance of about 1460cm-1Is reduced to about 90 ℃ to obtain a solution of chlorinated polyolefin (b) having no allyloxy group at a concentration of about 27%. Then, the blowing of air into the liquid phase was stopped, and the stirring was continued at about 90 ℃ while flowing nitrogen into the gas phase, and as a mixture of 197 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of ethylene glycol dimethacrylate, 2 parts of acrylic acid, and 5 parts of Perbutyl PV, 189.5 parts of toluene, and 63 parts of butyl acetate, as a compound (c) of 1 or more selected from the group consisting of (meth) acrylate, (meth) acrylic acid, and styrene, was added dropwise, and as a result, the reaction system gelled about 1 hour after the start of the addition, and the production of the polymer composition containing the modified chlorinated polyolefin was stopped.
Comparative example 2
A four-necked flask equipped with a cooling tube was charged with 100 parts of スーパークロン 3228S, 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. To this mixture, 23 parts of 2-hydroxyethyl methacrylate and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 23 parts of 2-hydroxyethyl methacrylate with an acid anhydride group. After about 40 minutes, the system suddenly heated and polymerization started, thus stopping the production of the polymer composition containing the modified chlorinated polyolefin.
Comparative example 3
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 218 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and heated to about 95 ℃ to prepare a solution. To this, 57.5 parts of 2-hydroxyethyl methacrylate, 2 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting the 2-hydroxyethyl methacrylate, butanol and acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1In a stage in which the absorbance ratio of (A) is substantially unchanged, cooling toAbout 90 ℃ to give a solution of chlorinated polyolefin (b) having no allyloxy group at a concentration of about 27%. The approximate molar ratio of 2-hydroxyethyl methacrylate reacted with the anhydride groups to butanol was 0.8/0.2. Then, while stopping blowing air into the liquid phase, the gas phase was continuously stirred at about 90 ℃ while flowing nitrogen gas, and as a mixture of 197 parts of methyl methacrylate, 186 parts of cyclohexyl methacrylate, 6 parts of 2-hydroxyethyl acrylate, 10 parts of styrene, 1 part of acrylic acid, 5 parts of Perbutyl PV, 189.5 parts of toluene, and 63 parts of butyl acetate was added dropwise as the compound (c) of 1 or more selected from the group consisting of (meth) acrylate, (meth) acrylic acid, and styrene, and as a result, the reaction system gelled about 1 hour after the start of dropping, and thus the production of the polymer composition containing the modified chlorinated polyolefin was stopped.
Comparative example 4
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and heated to about 95 ℃ to prepare a solution. 11.5 parts of 2-hydroxyethyl methacrylate, 17 parts of butanol and 0.1 part of tetrabutylammonium bromide were added thereto, and stirring was continued while reacting the 2-hydroxyethyl methacrylate, butanol and acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was lowered to about 90 ℃ while keeping the absorbance ratio of (a) to (b) substantially unchanged, and 180 parts of toluene was further added to obtain a solution of chlorinated polyolefin (b) having no allyloxy group and having a concentration of about 27%. The approximate molar ratio of 2-hydroxyethyl methacrylate reacted with the acid anhydride group to butanol was 0.1/0.9. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylate, (meth) acrylic acid and styrene, 197 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 2 parts of ethylene glycol dimethacrylate, 10 parts of styrene, 2 parts of acrylic acid, 5 parts of Perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate were added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixed solution of 197 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 2 parts of ethylene glycol dimethacrylate, 10 parts of styrene, 2 parts of acrylic acid, 5 parts of Perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate was added dropwise over about 1 hourA mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added thereto, and the mixture was stirred for about 1 hour and then cooled to room temperature to obtain a polymer composition (P-22) containing a modified chlorinated polyolefin. The resulting polymer composition (P-22) containing a modified chlorinated polyolefin had a solid content of about 46% and a hydroxyl value of the resin solid content of about 9 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton of about 20/80.
Comparative example 5
A four-necked flask equipped with a cooling tube was charged with 100 parts of "スーパークロン 822S", 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and heated to about 95 ℃ to prepare a solution. 11.5 parts of 2-hydroxyethyl methacrylate, 17 parts of butanol and 0.1 part of tetrabutylammonium bromide were added thereto, and stirring was continued while reacting the 2-hydroxyethyl methacrylate, butanol and acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was lowered to about 90 ℃ while keeping the absorbance ratio of (a) to (b) substantially unchanged, and 172 parts of toluene and 6.8 parts of 2-hydroxyethyl methacrylate were further added to obtain a solution of chlorinated polyolefin (b) having no allyloxy group and having a concentration of about 27%. The approximate molar ratio of 2-hydroxyethyl methacrylate reacted with the acid anhydride group to butanol was 0.1/0.9. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid ester, (meth) acrylic acid and styrene, a mixture of 206 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 2 parts of ethylene glycol dimethacrylate, 3 parts of methacrylic acid and 5 parts of Perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate was added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, continuing stirring for about 1 hour, and then cooling to room temperature to obtain a polymer composition (P-23) containing a modified chlorinated polyolefin. The solid content of the resulting polymer composition (P-23) containing a modified chlorinated polyolefin was about 46%, and the hydroxyl value of the resin solid content was about 15 mgKOH/g. In addition, make upThe composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton in the product was about 20/80.
Comparative example 6
A four-necked flask equipped with a cooling tube was charged with 50 parts of "ハードレン F-6P", 70 parts of toluene, and 0.05 part of di-t-Butylhydroxytoluene (BHT), and the mixture was stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ℃ to prepare a solution. 11.5 parts of 2-hydroxyethyl methacrylate, 16 parts of butanol, 1 part of 2-ethylhexanol, and 0.1 part of tetrabutylammonium bromide were added thereto, and stirring was continued while reacting 2-hydroxyethyl methacrylate, butanol, 2-ethylhexanol, and an acid anhydride group. In infrared absorption analysis of solid components in solution, at about 1770cm-1Absorbance of about 1460cm-1The temperature was lowered to about 90 ℃ to obtain a solution of chlorinated polyolefin (b) having no allyloxy group and having a concentration of about 16% by further adding 180 parts of toluene. The approximate molar ratio of 2-hydroxyethyl methacrylate reacted with the acid anhydride group to the other alcohols was 0.1/0.9. Then, as the compound (c) of 1 or more selected from the group consisting of (meth) acrylic acid ester, (meth) acrylic acid and styrene, a mixture of 214 parts of methyl methacrylate, 222 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of ethylene glycol dimethacrylate, 2 parts of acrylic acid, 5 parts of Perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate was added dropwise over about 4 hours while stopping blowing air into the liquid phase and continuing stirring at about 90 ℃ while flowing nitrogen into the gas phase, and a mixture of 5 parts of Perbutyl PV and 70 parts of toluene was added dropwise again over about 1 hour, and continuing stirring for about 1 hour, followed by cooling to room temperature, thereby obtaining a polymer composition (P-24) containing a modified chlorinated polyolefin. The resulting polymer composition (P-24) containing a modified chlorinated polyolefin had a solid content of about 46% and a hydroxyl value of the resin solid content of about 9 mgKOH/g. The composition had a composition ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton of about 10/90.
Production of coating compositions
Example 19
To a formulation prepared by uniformly mixing 100 parts of the modified chlorinated polyolefin-containing polymer composition (P-1) obtained in example 1 and 3.2 parts of "スミジュール N3300" (product name, manufactured by Tokyo コベストロウレタン, isocyanurate of hexamethylene diisocyanate, content of solid content: 100%, content of isocyanate: 21.6% by weight) was added 0.15 part of dibutyltin dilaurate as a catalyst, and further toluene and butyl acetate were added to adjust viscosity, thereby obtaining a coating composition No.1 having a viscosity of about 30 seconds as measured at 20 ℃ by Ford cup No. 4. The equivalent ratio (NCO/OH) of the isocyanate group in "スミジュール N3300" to the hydroxyl group in the resin component of the polymer composition (P-1) containing a modified chlorinated polyolefin was about 1.8.
Examples 20 to 36 and comparative examples 7 to 12
Coating compositions Nos. 2 to 24 each having a viscosity of 30 seconds as measured at 20 ℃ by a Ford cup No.4 were obtained in the same manner as in example 19 except that the compounding composition of the polymer composition containing a modified chlorinated polyolefin and the polyisocyanate compound in example 19 was as shown in Table 1 described later. In addition, comparative examples 7 to 9 failed to produce a coating composition because the polymer compositions ("P-19" to "P-21") containing a modified chlorinated polyolefin as a raw material could not be produced.
Each of the coating compositions obtained above was evaluated by the following test method. The evaluation results are shown in table 1 together with the paint composition.
[ Table 1]
TABLE 1
Figure BDA0002173612280000371
Test method
Manufacturing stability: the case where the polymer composition containing the modified chlorinated polyolefin could be produced was evaluated as "O", and the case where the polymer composition could not be produced was evaluated as "X".
Curability (gel fraction (gel content)): each coating composition was applied to a glass plate to a dry film thickness of 40 μm, and dried by heating at about 90 ℃ for 30 minutes. Subsequently, the coating film on the glass plate was collected and the mass (Wa) was measured. Then, the coating film was placed in a 200-mesh stainless steel mesh container, extracted under reflux in acetone heated to about 56 ℃ for 1 hour, the coating film mass (Wb) after drying at 100 ℃ for 1 hour was measured, and the remaining insoluble coating film percentage (mass%) calculated according to the following formula was used as the gel fraction to evaluate the curability in accordance with the following criteria.
Gel fraction (% by mass) of (Wb/Wa) × 100
A: gel fraction of 70% or more
B: the gel fraction is more than 60% and less than 70%
C: the gel fraction is more than 50% and less than 60%
D: the gel fraction is more than 30% and less than 50%
E: the gel fraction was less than 30%.

Claims (7)

1. A process for producing a polymer composition containing a modified chlorinated polyolefin, which comprises a step of copolymerizing a chlorinated polyolefin (b) having an allyloxy group with a polymerizable monomer containing at least 1 compound (c) selected from the group consisting of (meth) acrylic acid esters, (meth) acrylic acids and styrene in the presence of a compound (a) having an allyloxy group and a hydroxyl group to obtain a modified chlorinated polyolefin,
wherein the compound (a) having an allyloxy group and a hydroxyl group is a compound represented by the following general formula (I):
Figure FDA0003210325330000011
in the formula, R1And R2Each independently represents a branched alkylene group having 2 or 3 carbon atoms, m and n each independently represent a real number of 0 to 50, and the sum of m and n is a real number of 1 or more, and may have a block structure or a random structure.
2. The process according to claim 1, wherein the chlorinated polyolefin (b) having an allyloxy group is obtained by addition reaction of a chlorinated polyolefin (d) having an acid anhydride group with a compound (a) having an allyloxy group and a hydroxyl group represented by the general formula (I).
3. The process according to claim 1 or 2, wherein the compound (a) having an allyloxy group and a hydroxyl group is allyloxyethanol.
4. A polymer composition containing a modified chlorinated polyolefin, which is obtained by copolymerizing a chlorinated polyolefin (b) having an allyloxy group with a polymerizable monomer containing at least 1 compound (c) selected from the group consisting of (meth) acrylic acid esters, (meth) acrylic acids and styrene in the coexistence of a compound (a) having an allyloxy group and a hydroxyl group,
wherein the compound (a) having an allyloxy group and a hydroxyl group is a compound represented by the following general formula (I):
Figure FDA0003210325330000021
in the formula, R1And R2Each independently represents a branched alkylene group having 2 or 3 carbon atoms, m and n each independently represent a real number of 0 to 50, and the sum of m and n is a real number of 1 or more, and may have a block structure or a random structure.
5. A curable composition comprising the polymer composition according to claim 4 and a crosslinking agent reactive with a hydroxyl group.
6. A coating composition comprising the polymer composition of claim 4.
7. The coating composition of claim 6, further comprising a crosslinking agent reactive with hydroxyl groups.
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Publication number Priority date Publication date Assignee Title
WO2019082903A1 (en) * 2017-10-25 2019-05-02 日本製紙株式会社 Modified polyolefin resin composition and production method therefor
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5996136A (en) * 1982-11-25 1984-06-02 Dainippon Ink & Chem Inc Coating resin composition
JPH04161334A (en) * 1990-10-25 1992-06-04 Mitsubishi Petrochem Co Ltd Manufacture of laminate
JPH06199918A (en) * 1992-12-28 1994-07-19 Nippon Paper Ind Co Ltd Aqueous resin composition
JPH0859757A (en) * 1994-08-22 1996-03-05 Kansai Paint Co Ltd Resin composition for aqueous coating material
JP2002309161A (en) * 2001-04-11 2002-10-23 Toyo Kasei Kogyo Co Ltd Coating composition for polyolefinic resin and its manufacturing method
EP1801086A1 (en) * 2005-11-25 2007-06-27 Synthacon GmbH Synthesis of carbon acid amides
CN101402704A (en) * 2008-11-14 2009-04-08 沂源瑞丰高分子材料有限公司 Uses of allyloxy hydroxide sodium dimercaptosulphanate in PVC processing aid
CN103333571A (en) * 2013-06-24 2013-10-02 广州慧谷化学有限公司 Water-based antimicrobial moldproof hydrophilic paint for heat exchanger fin surface treatment
JP2015003991A (en) * 2013-06-20 2015-01-08 東レ・ファインケミカル株式会社 Coating modified chlorinated polyolefin resin composition and method for producing the same
JP2015059182A (en) * 2013-09-19 2015-03-30 新中村化学工業株式会社 Resin composition, adhesive agent and manufacturing method of resin composition
CN105111361A (en) * 2015-09-10 2015-12-02 江南大学 Preparation method of nanometer latex color paste for drawing materials
CN105693939A (en) * 2014-11-28 2016-06-22 合众（佛山）化工有限公司 Preparation method of SMA modified cationic acrylate emulsion for primers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6392041B1 (en) * 1999-02-25 2002-05-21 Ciba Specialty Chemicals Corporation Hydroxy-substituted N-alkoxy hindered amines and compositions stabilized therewith
JP4508635B2 (en) * 2003-12-26 2010-07-21 リンテック株式会社 Hard coat film for image display device

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5996136A (en) * 1982-11-25 1984-06-02 Dainippon Ink & Chem Inc Coating resin composition
JPH04161334A (en) * 1990-10-25 1992-06-04 Mitsubishi Petrochem Co Ltd Manufacture of laminate
JPH06199918A (en) * 1992-12-28 1994-07-19 Nippon Paper Ind Co Ltd Aqueous resin composition
JPH0859757A (en) * 1994-08-22 1996-03-05 Kansai Paint Co Ltd Resin composition for aqueous coating material
JP2002309161A (en) * 2001-04-11 2002-10-23 Toyo Kasei Kogyo Co Ltd Coating composition for polyolefinic resin and its manufacturing method
EP1801086A1 (en) * 2005-11-25 2007-06-27 Synthacon GmbH Synthesis of carbon acid amides
CN101402704A (en) * 2008-11-14 2009-04-08 沂源瑞丰高分子材料有限公司 Uses of allyloxy hydroxide sodium dimercaptosulphanate in PVC processing aid
JP2015003991A (en) * 2013-06-20 2015-01-08 東レ・ファインケミカル株式会社 Coating modified chlorinated polyolefin resin composition and method for producing the same
CN103333571A (en) * 2013-06-24 2013-10-02 广州慧谷化学有限公司 Water-based antimicrobial moldproof hydrophilic paint for heat exchanger fin surface treatment
JP2015059182A (en) * 2013-09-19 2015-03-30 新中村化学工業株式会社 Resin composition, adhesive agent and manufacturing method of resin composition
CN105693939A (en) * 2014-11-28 2016-06-22 合众（佛山）化工有限公司 Preparation method of SMA modified cationic acrylate emulsion for primers
CN105111361A (en) * 2015-09-10 2015-12-02 江南大学 Preparation method of nanometer latex color paste for drawing materials

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
乳液型CPP-g-MAH复膜胶的研制;项东升，等;《中国胶黏剂》;20130531;第22卷(第5期);第35-38,60页 *
聚烯烃功能化进展;张凯，等;《合成树脂及塑料》;20050430;第22卷(第2期);第66-69页 *

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