JPS60147418A - Antifouling composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent antifouling property and weatherability, etc., and composed mainly of a copolymer consisting of specific amounts of a vinyl monomer containing polyfluoroalkyl group, a specific organic silicon compound, and a vinyl monomer copolymerizable therewith. CONSTITUTION:The objective composition can be produced by copolymerizing (A) 0.1-98(wt)%, preferably 0.5-70% vinyl monomer containing polyfluoroalkyl group [e.g. the compound of formula CH2=C(CH3)CO2CH2CH2N(C3-H7)SO2C8 F17] with (B) 0.5-30%, preferably 1-15% organic silicon compound containing alkenyl group and a hydrolyzable group and/or hydroxyl group bonded to Si atom [e.g. the compound on formula CH2=CHC-O2(CH2)3Si(OCH3)3] and (C) 0-70% monomer copolymerizable with the components A and B (e.g. n-butyl methacrylate). EFFECT:It can be crosslinked at a low temperature and has excellent adhesivity. It can be applied by conventional method. USE:Facing material of large-sized construction, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antifouling composition, and particularly to an antifouling composition that has excellent stain resistance and weather resistance and is useful in obstetrics and other fields.

Various synthetic resin paints have been known for some time, but all of them are water repellent.

There are two problems with oil repellency, stain resistance, and oil resistance, and in recent years, improving the stain resistance performance of the exterior has become an issue, so fluororesin-based products are used for this purpose. However, since this generally requires high temperature direct coating conditions, there is a strong demand for a coating that can be coated near room temperature.

The present invention relates to an antifouling composition that satisfies such demands, and includes 1) a polyfluoroalkyl group-containing vinyl monomer of 0.1 to 98% by weight;

2) 0.5 to 30% by weight of an organic silicate compound containing an alkenyl group and 1:1 bonded hydrolyzable group and/or hydroxyl group in the molecule; 3) Copolymerization with the above 1) and 2). The main ingredient is a copolymer consisting of 0 to 70% by weight of a vinyl monomer having properties.

Namely, the present inventors have conducted various studies on the modification of vinyl paints and % senior acrylic paints.

As a vinyl resin component, a vinyl monomer containing a fluoroalkyl group in its molecule is used, and this is bonded to an alkenyl group and a silicon atom to form an organic silicone compound having a hydrolyzable group and/or a hydroxyl group. It was discovered that the coating film obtained from the composition obtained by copolymerizing the compound with the compound has excellent weather resistance, stain resistance, water repellency, and oil repellency. The present invention was completed based on the discovery that low-temperature crosslinking is possible because it contains a decomposable organosilicon group or silanol group, and furthermore, it has good adhesion to various substrates.

The gt acid component of the copolymer constituting the composition of the present invention is a vinyl monomer containing a polyfluoroalkyl group, and this fluoroalkyl group is a methyl group.

Ethyl group - alkyl group such as glopyl group, butyl group, octyl group, etc. Any group in which part or all of the hydrogen group bonded to C2 may be substituted with a fluorine atom is sufficient, and this direct: is the following formula % formula %) ) is exemplified by fluoroalkyl group-containing acrylic acid or methacrylic acid, but this may also be a derivative represented by the following formula % ) ) ) (n is an integer from 1 to 1O) - Commonly, these include the reaction of a linear monobranched fluorinated alcohol with an acid chlorine or other agent, or the reaction of a linear or branched fluorinated carboxylic acid or its acid halide with β- and droxyethyl (meth)acrylate. It can be obtained by known synthetic methods such as reaction with methane acrylic acid chloride, and further reaction with fluorinated alkanesulfonic acid amide having a hydroxyaldP group.

If the component ratio of this polyfluoroalkyl group-containing vinyl monomer in g2 in the copolymer is less than 0.1 weight ratio, a sufficient effect cannot be expected; Although the effect can be expected, the crosslinkability of this copolymer is insufficient and the mechanical properties and solvent resistance of the resulting coating film deteriorate. 0.5 to 70 weight! Although it is required to be 1%, this may be used alone or as a mixture of two or more types.

In addition, the organosilicon compound as the second component constituting this copolymer contains an alkenyl group and a silicon atom in its molecule for copolymerization with the polyfluoroalkyl group-containing vinyl spinning wheel body as the first component. It is essential to have a hydrolyzable group and/or a hydroxyl group bonded to. Examples of this hydrolyzable group include acyloxy groups such as acetoxy, octanoyloxy, and benzoyloxy groups; ketoxime groups such as dimethylketoxime, methylneethylketoxime, and diethylketoxime; methoxy groups; Alkoxy groups such as ethoxy group and globoxy group, ingropenyloxy group, l-ethyl-2-
Alkenyloxy groups such as methylvinyloxy group, amino groups such as dimethylamino group, diethylamino group, butylamino group, cyclohexylamino group, and dimethylaminoxy group.

Aminoxy groups such as diethylaminoxy groups, N-methylacetamide groups, N-ethylacetamide groups.

It must contain an amide group such as an N-methylbenzamide group, so it must be electronically stable.

It is best to avoid substances that are highly harmful to the bean body and substances that produce high boiling point substances after hydrolysis.

This organosilicon compound has the following formula: 0 formula% ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) OH=casi(oOan3),.

2 C5=O) 181 (OH) (00H).

2 3! 2B 0H2=OH81(0H1), I810H3(0OH
3)z.

1 0H=OH810H (OOOH).

2 25- 32 0H=ausau (ON(OH3)O,H,)2j
13 or a partial hydrolyzate thereof, but it is preferably a derivative of acrylic acid or methacrylic acid.

These are for example acrylic acid or methacrylic acid.

Addition reaction of allyl or acetylene with trichloroacetylene, trimethoxysilane, etc. and subsequent carboxylic acid,
It can be synthesized by a known reaction with alcohol or the like.

If the component ratio of this organosilicon compound in the copolymer is less than 0.5 weight ts, the coating film obtained from this copolymer will not show sufficient performance, and if it exceeds 30 weight ts, the crosslinking density will increase. If it is too high, the membrane becomes brittle and there is a risk that it will form a gel during one polymerization reaction.

The weight range is preferably from 0.5 to 30% by weight, more preferably from 1 to 15% by weight.

Next, the vinyl monomer as the third component of the copolymer constituting the composition of the present invention determines the strength, hardness, adhesion to the substrate, stain resistance, etc. of the copolymer film. It is said to be an optional component added in the same manner as above, and includes methyl (meth)acrylate, ethyl (meth)acrylate,
n-butyl (meth)acrylate, 1-butyl (meth)
Acrylate, 2-ethyl(meth)acrylate
7 acrylates, methacrylates, acrylates containing silicon groups such as r-tris(trimethylsiloxy)silylglopyll(meth)acrylate, r-bis(trimethylsiloxy)methylsilylglopyll(meth)acrylate, methacrylates, N,N -dimethylaminoethyl (methaneacryle), N,N-diethylaminoethyl (meth)acrylate, etc., or glycidyl (
Epoxy group-containing acrylates and methacrylates such as meth)acrylates1 containing polyoxyethylene groups and polyoxygumipyrene groups with a molecular weight of 100 to 1.0001
(Meth)acrylates in which one end is blocked with a methyl group, ethyl group, butyl group, phenyl group, etc., general formula %) \C2R is a hydrogen atom or a methyl group, R is a monovalent hydrocarbon group, n=an integer of 2 to 20) (methane acrylates, styrene, aromatic vinyl compounds such as vinyltoluene, unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and carbon atoms of 1 to 18). Diesters with monohydric alcohols.

Y V ia acid anhydride, n-7” thyl vinyl ether.

Vinyl ether A/ such as cyclohexyl vinyl ether
Examples include the following, and these are arbitrary (
:l A single-layer plate is used, but vinyl monomers with active hydrogen groups such as β-hydroxy≠ethyl (meth)acrylate, (meth)acrylic acid β-methylol-acrylamide, etc. are copolymerized. Its use should be avoided as it may cause medium gelatinization.

The copolymer which is the main component of the composition of the present invention is as described above.
) to 3) can be obtained by copolymerizing the monomers as components by a known method such as solution polymerization using a radical reaction initiator. Examples of this radical reaction initiator include azobisiso-butyminitrile, di-t-butyl peroxide, dibensoyl peroxide, t-butyl perbenzoate, and methyl ethyl ketone peroxide. The reaction is preferably carried out in organic solvents such as group hydrocarbons, acetate esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and in some cases methanol, ethanol, and glopanol.

The reaction may be carried out in a mixed solvent of a lower monohydric alcohol such as butanol and the above solvent, or in the presence of a chain transfer agent such as mercaptans.

The composition of the present invention is usually provided as a solution of the above-mentioned copolymer in an organic solvent. A catalyst may also be added.

The composition of the present invention can be used as it is as a clear paint, but it can also be used as an enamel paint with added pigments, and can also be dried and flexible as required.

To improve solvent resistance? Cellulose compounds such as dinitrocellulose, plasticizers such as polyester resins, and paint additives such as leveling agents and ultraviolet absorbers may also be added.

The composition of the present invention can be applied to various exteriors, special zone two large-scale accommodation buildings and high W
It is useful for painting buildings, architectural structures, automobiles, home appliances, road signs, guardrails, etc. Applications to this object can be applied by coating, spray painting, etc.
It can be applied by a special method such as a-ru coating, which cannot be used with conventional fluorocarbon resins, and it is possible to easily obtain a self-adhesive coating film using C2.

In addition to the above, the composition of the present invention can also be used for m-ray treatment, and when used in combination with various resins for fiber treatment, the organic silicon group imparts affinity and durability to fibers. This treatment method (spraying method, dipping method, etc.) can be used. r Next, examples of the present invention will be given. The results of the @Russia model experiment and its evaluation method in C2C are shown in 5 below.

[Exposure model experiment method]

A glass plate coated with a 5% trichloro-a-ethane solution of the copolymer compositions obtained in Examples and Comparative Examples 1
After heat treatment at 50°C for 1 hour, this was mixed with 40 parts of sand, 20 parts of clay, 25 parts of silica, and 12 parts of mineral oil.

Shake several times in a dry oil consisting of 3 parts of carbon, then spray with approximately 300% water using a water repellency measuring spray to wash away dirt, and dry at room temperature. 'I repeated this 10 times as a cycle.

,〔Evaluation methods〕 Evaluation is done by measuring light transmittance using a haze meter.

This was done based on the difference between the initial state and the state after stains were removed.

, △Tt...Effect of light transmittance (Tt) △Haze...Change in degree (haze value)◎ ・・・・・・・・・
・No dirt remains O: Slight dirt remains △ River: Very noticeable dirt: X: Dirt is noticeable, Example 1: The entire surface is cloudy. A four-loop flask (2, methyl ethyl ketone 10
Prepare 0 parts and 10 parts of azobisisobutyronitrile and make 80
The temperature was raised to ℃. Then, N-n-g a pyruperfluoro a octanesulfonic acid amidoethyl arylate 0, H2 (OR=OHOO(OH) N-800F)! 22
2 A mixed solution consisting of 800 parts of 281F - 20 parts of r'-(')rimethoxysilyl) daguchivir acrylate, 370 parts of n-butyl methacrylate, and 420 parts of methyl ethyl ketone was added dropwise over 5 hours. When stirred at temperature,
A colorless and transparent resin solution with a non-volatile content of 7 (l) was obtained.

Next, exposure model experiments were conducted on these two resin solutions, as well as weather resistance tests in a sunshine waterometer, which are shown in Tables 1 and 2 below. Q(
2. The results were as described.

Example 2 80 parts of methyl ethyl ketone and 10 parts of azobisisobutyronitrile were charged into the same apparatus as in Example 1, and the temperature was raised to 80°C. (Triacetoxysilyl/I/
) globil methacrylate 20 flS, n-butyl methacrylate) 380 fflS and methyl ethyl ketone 3
60 parts of the mixture was added dropwise over 5 hours and stirred at the same temperature for an additional 10 hours to obtain a colorless and transparent resin solution with a non-volatile content of 70 parts.

Next, two resin bath wigs were used as in Example 1:
When an exposure model experiment was conducted and its weather resistance was investigated, the results as shown in Table 1 and Table 2 C2, which will be described later, were obtained.

Example 3 Same equipment as Example 1 C 150 parts of dimethyl ethyl ketone,
Charge 10 parts of azobisisobutyronitrile and raise the temperature directly to 80℃, add 2, 2.3, 3, 4.4, 5, 5.5
-nonafluoropentyl methacrylate-) 600 parts, γ-
A mixture consisting of 20 parts of [(jetoxy)methylsilyl]globil methacrylate, 270 parts of methyl methacrylate, 100 parts of ethyl acrylate, and 350 parts of toluene was added dropwise over 5 hours, followed by stirring at the same temperature for an additional 2 hours. A resin solution with a non-volatile content of 50 yen was obtained, and the same g:@Ru model experimental weatherability test as in Example 1 was conducted on this solution, as shown in Table 1 below.
The results as listed in Table 2 were obtained.

Example 4 200 parts of methyl ethyl ketone and 10 parts of azobisisobutyronitrile were charged into the same apparatus as in Example 1, and the temperature was raised to 80°C. 0H20
H,-TO0OC1,F1s' 250 ftL A mixture consisting of 10 parts of methyl di-methoxysilane, 20 parts of γ-(triethoxysilylonpropyl methacrylate-210 parts of methyl methacrylate and 300 parts of methyl ethyl ketone) was added dropwise over 5 hours. When the solution was further stirred for 10 hours at the same temperature during the incubation, a transparent resin solution with a non-volatile content of 50% was obtained.Exposure model experiments and weather resistance tests were conducted on this in the same manner as in Example 1, and the results will be described later. 8g The results as shown in Tables 1 and 2 were obtained.

Example 5 320 parts of toluene and 10 parts of azobisisobutyronitrile were charged in the same apparatus as in Example 1, and 500 parts of 2N-n-globil (perfluorooctane sulfonamide) ethyl acrylic acid, r- (Trimethoxytolyl) 20 parts of propyl methacrylate, methylpolyoxyethylene acrylate (OH=OHOOCOOHOH)O
OH, molecular weight 11 2 2Q a -500) 200 parts, ethyl methacrylate 67 os
,)kzy800 Kfik'J,hi1 7"//-
A mixture consisting of 280 parts of 280 parts of resin was added dropwise at 80°C over 5 hours, and the mixture was further stirred at the same temperature for 10 hours. A transparent resin solution with a non-volatile content of 50 was obtained. When the @vaporizer experiment and the weather resistance test were conducted in the same manner as in 1, the results shown in Tables 1 and 2 below were obtained.

Comparative Example 1 300 parts of toluene and azobisisobutyronitrile 10i1S were charged into the same reactor as in Example 1, and the temperature was raised to 80°C, and 370 parts of methyl acrylate, 200 parts of methyl methacrylate, A mixture consisting of 20 m of silyl) g(pyrmethacrine) and 300 parts of toluene was added dropwise over 5 hours, and stirring was continued for 3 hours at the same temperature. A resin solution with a nonvolatile content of 501 was obtained. An exposure model experiment and a weather resistance test were conducted in the same manner as in Example 1.

The results shown in Table 1 and Table 2 below were obtained. - Comparative Example 2 In the same reaction apparatus as in Example 1, 300 parts of toluene and 10 parts of azobisisobutyronitrile were charged.

180 parts of diethyl acrylate, 360 parts of ethyl methacrylate, and r-()rimethoxytrile.

) 30 parts of probyl methacrylate and 300 parts of toluene
When a mixture consisting of 1 and 2 parts was added dropwise at 80°C over 5 hours and further stirred at the same temperature for 3 hours, a resin solution with a nonvolatile content of 50- Similarly, an exposure model experiment and a weather resistance test were conducted, and the results shown in Table 1 and Section 2 below were obtained. 10 parts of bisisobutyronitrile were charged, and the temperature was raised to 100°C, followed by 280 parts of Niethyl acrylate and 280 parts of n-butyl methacrylate.

30m vinyltriacetoxysilane and 40m toluene
A mixture consisting of 0 parts was added dropwise over a period of 5 hours.

After further stirring at the same temperature for 5 hours, a resin solution with a nonvolatile content of 50 g was obtained.
: When an exposure model experiment and a weather resistance test were conducted, the results shown in Table 1 and Section 2 below were obtained.

Table 2 Weather resistance test results

Claims (1)

[Scope of Claims], 1.1) YN trifluoroalkyl group-containing vinyl monomer 0.1 to 98% by weight 2) L-nialkenyl group and silicon atom (two-bonded hydrolyzable group and or A copolymer consisting of a hydroxyl group-containing organosilicon compound 0.5-30% by weight 3) and a copolymerizable vinyl monomer 0-70% by weight as the main ingredient. An antifouling composition characterized by: