JPS6037130B2 - Crosslinking method for hydrophilic copolymers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a room-temperature crosslinking method for a hydrophilic acrylic copolymer containing 2 to 9% by weight of an ethylenically unsaturated monomer having a tertiary amino group as a functional group. It is.

Acrylate or methacrylate polymers having hydroxyl groups as side chains are insoluble in water, although they are hydrophilic.

Therefore, by utilizing this hydrophilic property, by coating the surface of an article made of another substance with the polymer, the surface of the article can be made hydrophilic. However, when this polymer alone absorbs water, its strength is very weak, and when the painted surface is rubbed with a finger, it crumbles and immediately peels off. Therefore, when using this polymer, organometallic compounds such as ammonium lithium, potassium, or sodium salts of chromic acid or other tetraisopropylaluminum are commonly used.

However, although these are said to be able to be used at normal humidity, they require long-term standing, heating, or light irradiation in order to be completely crosslinked.
In order to improve these drawbacks, the present inventor focused on isocyanates as a result of intensive research.

However, it is well known that isocyanate groups react very well with hydroxyl groups, but it does not only react with polymers having hydroxyl groups, but also rapidly reacts with the hydroxyl groups of gutter solvents. However, since it does not substantially contribute to the crosslinking reaction of the polymer, the strength of the film obtained by coating the polymer mixture upon absorption of water is not improved at all. The most important point of the present invention is that 2 to 9 units by weight of ethylenically unsaturated monomers having tertiary amino groups as functional groups 5 to 95 weight % acrylates or methacrylates having hydroxyl groups
and the remainder consists of other copolymers.Solvents for hydrophilic copolymers include not only polar solvents but also aromatic systems such as benzene, toluene, and xylene, esters such as ethyl acetate and butyl acetate, methyl ethyl ketone, methyl propyl ketone, and methyl. Ketones such as butyl ketone diethyl ketone, dimethyl formamide, dimethyl sulfoamide,
It is now possible to select from aprotic polar solvents such as nitrogen compounds such as IY methylpyrrolidone, which has traditionally been widely used as a solvent for hydrophilic polymers.

. The point is that crosslinking of the copolymer with isocyanate groups is realized because no tonic polar solvent is used. Since the reaction between isocyanate groups and hydroxyl groups is rapid even at room temperature, the crosslinking reaction proceeds completely without the use of auxiliary measures such as heat or light, unlike the reaction between hydroxyl groups and dichromate.

Therefore, the crosslinked coating of the present invention maintains a high degree of coverage even after drying for just one hour after application, and even after absorbing water, its adhesion to the substrate and strength are greatly improved, making it suitable for practical use even when it has sufficiently absorbed water. I was able to withstand it. The ethylenically unsaturated monomer having a tertiary amino group constituting the copolymer of the present invention has the general formula 1cH2,000RI/R3COOR2B (1) R4 (wherein, R is a hydrogen atom or methyl group, R2
is an alkylene group having 1 to 12 carbon atoms, and R3 and R4 are alkylene groups having 1 to 12 carbon atoms.

), which is present in the copolymer in an amount of 2 to 90% by weight, preferably 10 to 8% by weight, most preferably 10 to 6% by weight. Examples include dimethylaminomethyl acrylate, diethylaminomethyl acrylate, di-n-propylaminomethyl acrylate, and diisop. pyraminomethyl acrylate, di-butylaminomethyl acrylate, diisobutylaminomethyl acrylate, di-SeC-butylaminomethyl acrylate,
Dibentylaminomethyl acrylate, dioctylaminomethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, di-n-
Propylaminoethyl acrylate, diisopropylaminoethyl acrylate, di-butylaminoethyl acrylate, diisobutylaminoethyl acrylate, dibentylaminoethyl acrylate, dihexylaminoethyl acrylate, dimethylamino-n-propyl acrylate, diethylamino- n-propylacrylate, di-n-bropylamino-n-bropylacrylate, diisopropylamino-n-propyl acrylate, dihexylamino-n-propyl acrylate, dimethylaminoisopropyl acrylate, diethylaminoisopropyl acrylate, di-n-propylaminoisopropyl acrylate , dibutylaminoisopropyl acrylate, dimethylamino-n-butyl acrylate, diethylamino-n-butyl acrylate,
Dimethylaminoisobutyl acrylate, dimethylaminoisobutyl acrylate, dimethylaminobentylacrylate, diethylaminooctyl acrylate, dimethylaminomethyl methacrylate Di-n-butylaminomethyl methacrylate, diisobutylaminomethyl methacrylate, di-sec-phthylaminomethyl methacrylate, di-octylaminomethyl methacrylate, dimethyl aminoethyl methacrylate,
Diethylaminoethyl methacrylate, di-n-propylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, di-n-butylaminoethyl methacrylate, diisobutylaminoethyl methacrylate, dihexylaminoethyl methacrylate, dimethylamino-n-propylacrylate, diethylamino-
n-propyl methacrylate, di-n-propyl amide/
-n-propyl methacrylate, diisopropylamino-n-propyl methacrylate, dibentylamino-n
-Propyl methacrylate, dimethylaminoisopropyl methacrylate, diethylaminoisopropyl methacrylate, Z-F. Lopylaminoisof. ropi/remethacrylate, dibutylaminoisopropyl methacrylate, dimethylamino-n-butyl methacrylate,
Diethylamino-n-butyl methacrylate, di-buty-reamin-n-buty/remethacrylate, diisobutylami/-n-butyl methacrylate, dimethylaminoisobutyl methacrylate, diethylaminoisobutyl methacrylate, dimethylaminobentyl methacrylate, diethylaminooctyl methacrylate, etc. . The acrylate or methacrylate having a hydroxyl group constituting the copolymer has the general formula □
(However, in the formula, R5 is a hydrogen atom or a methyl group, R5
is an alkylene group having 2 to 6 carbon atoms, m is 0 to 1
n is an integer from 1 to 14.

), which is present in the copolymer in an amount of 5 to 95% by weight, preferably 2
It contains from 0 to 9% by weight, most preferably from 30 to 90% by weight. Examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxybutyl acrylate,
Hydroxyhexyl acrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, tetraethylene glycol monoacrylate, diph. Ropylene glycol monoacrylate, tripropylene glycol monoacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2
-Hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monomethacrylate, dibropylene glycol monomethacrylate, tribropylene glycol monomethacrylate Examples include methacrylate. Furthermore, the copolymerizable monomers contained as a remainder in the copolymer include ethylenically unsaturated monomers other than those mentioned above.

For example, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, 2-
Alkyl acrylates such as ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate,
Alkyl methacrylates such as lauryl methacrylate, cyclohexyl acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, unsubstituted or N-alkyl substituted acrylamide or methacrylamide, such as N-propylmethacrylamide, diacetone acrylamide, aminoalkyl acrylate, such as 2-aminoethyl acrylate, 3-aminopropyl acrylate, 4-aminobutyl acrylate, etc. , aminoalkyl methacrylates such as 2-aminoethyl methacrylate, 3-aminopropyl methacrylate, 4-aminobutyl methacrylate, vinyl acetate, styrene, and the like. The copolymer of the present invention can be obtained by any method such as casting syrup or by bulk polymerization to obtain a polymer and dissolving it in an appropriate solvent, or by solution polymerization or suspension polymerization in a solvent. A method will be explored.

Polymerization is carried out in the presence of a radical polymerization catalyst, usually at 50 to 14
0qo, preferably at a temperature of 60-120°C for 1-2 feeding hours, preferably 9-1 feeding hours. As the radical polymerization catalyst, tert-butyl/g-octoate,
Examples include benzoyl/gu oxide, isopropyl perponate, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl/gu oxide, and azobisisobutyronitrile. Intrinsic viscosity of the thus obtained copolymer measured by a capillary viscometer
The measurement result of (d'/night) is 0.1 to 1.5, preferably 0.35 to 1.0. In addition, solvents include ketones such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, and diethyl ketone, aromatic compounds such as benzene, toluene, and xylene, esters such as ethyl acetate, butyl acetate, dimethyl formaldehyde, dimethyl sulfur acid, etc. It is necessary to use a solvent such as a nitrogen compound such as , N-methylpyrrolidone or a mixture of two or more thereof.

A monomer or polymer compound having two or more isocyanate groups at the end of the molecule, which is used as a crosslinking agent, is used in an amount of 3 to 3 parts by weight per 100 parts by weight of the copolymer.
10 parts by weight are preferably used, preferably 5 to 50 parts by weight, most preferably 10 to 3 parts by weight.

Typical crosslinking agents include the following: tolylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, or a polymer compound derived from these with two or more isocyanate groups. For example, Coronatore, Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.)
Desmodule L, Desmodule U, Desmodule IL, Desmodule HL (manufactured by Bayer), etc. are used. By mixing these isocyanate compounds into the polymer solution, the crosslinking reaction proceeds. The coating obtained according to the invention is a pre-applied anti-fouling topcoat and an unsaturated Demonstrates sufficient adhesion to polyester resin-glass fiber laminates.

The thickness of the coating applied will vary depending on the particular composition used and the method of application.

The thickness is usually 10 to 50 mm, preferably 30 to 20 mm.
It's a cry. The coating is applied to the surface of the coating by any method such as brushing, dipping, spraying, rolling, etc. The thus applied coating is dried at room temperature for 1 to 2 hours, preferably for 2 to 1 hour, to complete the crosslinking reaction.

Of course, the crosslinking time can also be accelerated by heating. The coatings obtained in this way are water-insoluble and have a water absorption of 10 to 200% by weight. Next, the present invention will be explained in more detail with reference to Examples.

In addition, all parts in the following examples mean parts by weight unless otherwise specified. Example 1 To a flask equipped with a thermometer, a thermometer and a reflux condenser were added 2 parts of dimethylamino/butyl methacrylate, 5 parts of hydroxyethyl methacrylate, 3 parts of butyl acrylate, and 40 parts of butyl acetate. 0.3 part of bisisobutyronitrile was added as a catalyst and reacted at 80 qo for about one hour to obtain a syrup-like liquid.

The resulting syrup contains 20% polymer content.

Add 20 tons of this syrup 100 Giko Coronate L (manufactured by Nippon Polyurethane Co., Ltd.) (polymer content: 75%, isocyanate content: 12.7-13.7%) and mix well. An aluminum disk with a diameter of about 20 arcs was coated with Lapacx No. 2 paint (ship bottom paint manufactured by China Paint ■), and a coating with a thickness of about 2 capes was obtained. This top-coated disc was left at room temperature for about 2 hours, then immediately immersed in water for 240 min. p. Although the top coat was rotated at m, the top coat did not peel off, and it did not peel off even when rubbed strongly with fingers. Meanwhile, the coating composition described above was poured onto a chrome plated plate to obtain a coating 0.5 sail thick. This was soaked in water for one week, then dried at 130°C for 2 hours, and the water absorption rate was measured and found to be about 40%. Example 2 Into the same flask as in Example-1, 40 B of dimethylformaside was added as a solvent to the base of dimethylaminoethyl methacrylate 3, 2-hydroxyethyl methacrylate 4, and lauryl methacrylate 3, and this was further added. 0.3 part of azobisisoputilonitrile was added as a catalyst to the mixture, and the reaction was carried out at 8,000 for about 1 hour to obtain a syrup-like liquid.

The resulting syrup contains 20% polymer content.
20 tons of this syrup 100% Cocoronate L (manufactured by Nippon Polyurethane Co., Ltd.) was added, and the mixture was thoroughly heated and tested in the same manner as in Example 1, but no peeling was observed.

Moreover, the water absorption rate was 60%. Example 3 Into the same flask as in Example-1, 40 parts of dimethylfluoramide was added to 2 parts of dimethylaminoethyl methacrylate and 80 parts of 2-hydroxyethyl methacrylate, and 0.3 part of asopisisobutyronitrile was added. was added as a catalyst, and a syrupy liquid was obtained by causing a reaction of about 106 Terama at 80o0.

The resulting syrup contains 20% polymer.

This syrup 100 Noko Coronate HL (manufactured by Nippon Polyurethane Co., Ltd. Polymer content 75% Isocyanate content 12.7-1
The same test as in Example 1 was conducted with 3M added (3.7% content), but there was no peeling at all. Also, the water absorption rate is 1
It was 20%.

Example 4 In a flask similar to Example 1, 10 parts of methacrylic acid and 2 parts of dimethylaminoethyl methacrylate were added.

xyethyl methacrylate 4, lauryl methacrylate 3, 40 xylene as a solvent, 0.3 part of azobisisobutyronitrile as a catalyst, and reacted at 8000 for about 1 hour to form a syrup-like product. Got the liquid. The resulting syrup contains 20% polymer.

To this syrup, diphenylmethane diisocyanate was dissolved in xylene to make a solution of about 20%, and this was added to the polymer in the syrup so that it became 10%.
A test similar to 1 was conducted. No peeling was observed at all. Moreover, the water absorption rate was 40%. Example 5 10 parts of methacrylic acid, 3 parts of dimethylaminoethyl methacrylate, 2 parts of butyl acrylate, 2 parts of butyl acrylate, 40 parts of butyl acetate as a solvent were added to 40 parts of 2-hydroxyethyl methacrylate, and then 40 parts of butyl acetate was added as a catalyst. Add 0.3 part of azobisisobutyronitrile to 800
The reaction was carried out for about 1 hour to obtain a syrup containing 20% of the polymer.

A test similar to that in Example 1 was conducted by adding 4 tb of metaphenylene diisocyanate to 100 g of this syrup, but no peeling was observed.

The water absorption rate was 100%.

Comparative Example 1 To the syrup 100 obtained in Example 2, two tats of an aqueous solution containing 20% ammonium dichromate were added, mixed well, and applied to the same disc as in Example 1 and dried at room temperature for about 2 hours. When it was later immersed in water, it immediately swelled and peeled off from the base.

Comparative Example 2 A test similar to that of Comparative Example 11 was carried out by leaving the product at room temperature for about 2 hours, but the results were the same as Comparative Example 11.

Comparative Example 3 The drying time of Comparative Example 2 was further extended and the drying time was left at room temperature for about 5 hours. p. When the disk was rotated in water at m, some peeling was observed, and when rubbed with a finger, it peeled off completely.

As in Example 1, syrup was poured onto the chrome plated slope and after drying for about one week, the water absorption rate was measured and found to be about 80%.

Example 6 95 parts of 2-hydroxyethyl methacrylate and 5 parts of dimethylaminoethyl methacrylate were added to the same flask as in Example 1, and 40 parts of dimethyl formamide was added as a solvent, and 0.0 parts of azobisobutyronitrile was added as a catalyst.
The mixture was added in batches and reacted at 80 qo for about 10 hours to obtain a syrupy liquid.

When 10 parts of this syrup and 2 parts of Coronate were added and the same test as in Example 1 was conducted, there was no peeling at all.

Moreover, the water absorption rate was 40%.

Claims (1)

[Claims] 1 (a) 2 to 90% by weight of an ethylenically unsaturated monomer having a tertiary amino group as a functional group; (b) 5 to 95% by weight of an acrylate or methacrylate having a hydroxyl group, with the remainder being covalent with the monomers mentioned above. Crosslinking of a hydrophilic copolymer characterized by reacting a copolymer composed of other polymerizable monomers with an isocyanate compound having two or more isocyanate groups at the end of the molecule in an aprotic polar solvent. Method.