JPH0242866B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new and useful resin composition for lacquer, and more particularly, it relates to a specific fluorine-containing resin, which is a perfluoroalkyl group- or fluoroalkyl group-containing vinyl (co)polymer, and a cellulose-based resin composition. Compounds as essential components and, if necessary, further using known and commonly used pigments, paint additives, or plasticizers, and which have particularly excellent water repellency, stain resistance, and weather resistance. It is. In recent years, acrylic paints have been used in a variety of fields due to their outstanding performance, but the performance required is also diverse.
Particularly recently, the requirements for weather resistance, water repellency, and stain resistance have become even higher in the fields of automobiles, home appliances, and exteriors.
The appearance of something even higher grade than the current one is eagerly awaited. However, the inventors of the present invention have conducted intensive studies to obtain vinyl-based paints that meet the above-mentioned requirements, especially acrylic lacquers with high practical value. The present invention was completed based on the discovery that a polymer or copolymer obtained using a cellulose compound can surprisingly, indeed dramatically improve the above-mentioned required performances when combined with a cellulose compound. I've come to the point where I can. That is, in the present invention, as essential components, 0.1 to 100% by weight of the perfluoroalkyl group or fluoroalkyl group-containing vinyl monomer (a), and other components copolymerizable with the vinyl monomer (a). vinyl monomer
(co) obtained by radical (co)polymerizing 0 to 99.9% by weight of (b) in the presence of a radical generator.
Comprising a polymer (A) and a cellulose compound (B),
The present invention provides a resin composition for lacquer, which further contains a plasticizer (C), if necessary. Here, the vinyl monomer (a) is a monomer having 1 or more carbon atoms in which hydrogen atoms are replaced with fluorine atoms.
It refers to a compound having a perfluoroalkyl group or a fluoroalkyl group preferably having 2 to 18 carbon atoms and a copolymerizable unsaturated double bond, and in the present invention, such a (per) Any compound having both a fluoroalkyl group and an unsaturated bond can be used, but representative examples include:
_CH2 = _{CHCOOCH2CF3 , CH2} =C( _CH3 )
COOCH ₂ CF ₃ , CH ₂ = CH ₂ COOCH ₂ CF ₂ CHF ₂ ,
CH ₂ =C(CH ₃ )COOCF ₂ CHF ₂ , CH ₂ =
CHCOOCH (CH ₃ ) - _{C 2} F ₅ , CH ₂ = C (CH ₃ )
COOCH (CH ₃ ) C ₂ F ₅ , CH ₂ = CH−COOCH
( _CF3 ) ₂ , _CH2 =C( _CH3 )COOCH( _CF3 ) ₂ , _CH2
＝CHCOOCH ₂ CF ₂ CHFCF ₃ , CH ₂ =C(CH ₃ )
COO―CH ₂ CF ₂ CHFCF ₃ , CH ₂ =CHCOOCH
( _CH3 ) _{C3F7 , CH2} =C( _CH3 )COOCH( _CH3 )
_{C3F3 ,} CH ₂ = CHOCH ₂・CH ₂ (−CF ₂ ) − ₉ CF ₃ , C ₄ H ₉ OOC・CH＝CH・COOCH ₂ C ₈ F ₁₇ or
In addition to C ₃ F ₇ OOC・CH=CHCOOCH ₂ C ₄ H ₉ , there are vinyl ethers or vinyl esters having a perfluoroalkyl group or a fluoroalkyl group. Reacting a fluorinated alcohol with a chain with an unsaturated carboxylic acid such as acrylic acid or methacrylic acid or their acid chloride, or reacting a fluorinated alkane carboxylic acid with a linear or cyclic chain or those acids. Reacting chloride with a hydroxyl group-containing vinyl monomer such as β-hydroxyethyl (meth)acrylate or β-hydroxypropyl (meth)acrylate, or reacting ethylene chlorohydrin adduct of fluorinated alkanesulfonic acid amide with acrylic It can be obtained by a known synthetic method such as reacting an acid, an unsaturated carboxylic acid such as methacrylic acid, or an acid chloride thereof. Of course, these can be used alone or as a mixture of two or more. If the usage amount of vinyl monomer (a) as listed above is less than 0.1% by weight (hereinafter simply abbreviated as %), the dramatic effect of the monomer will inevitably be lost. It is unpredictable, therefore,
The amount of the monomer used may range from 0.1 to 100%, taking into account both the effect of using the monomer and the solubility of the resulting (co)polymer in an organic solvent. In some cases, the range of 0.1 to 90% is particularly preferable. On the other hand, typical monomers that can be used as the vinyl monomer (b) include styrene,
Aromatic vinyl compounds such as vinyltoluene or α-methylstyrene; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate or i-butyl (meth)acrylate Class; unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid and C ₁ to C ₁₈ 1
Diesters with alcohols; vinyl esters such as vinyl acetate or vinyl benzoate;
(meth)acrylamides such as (meth)acrylamide, dimethyl (meth)acrylamide or N-alkoxymethylated (meth)acrylamide; N,N-dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate; Phosphoric acid group-containing (meth) such as β-acid phosphooxy (meth)acrylate
Acrylates; unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, fumaric acid or itaconic acid, or equimolar addition reaction products of hydroxyl group-containing vinyl monomers and saturated polycarboxylic acids; glycidyl (meth)acrylate; Methyl glycidyl (meth)acrylate or (meth)allyl glycidyl ether or unsaturated carboxylic acids such as the above-mentioned (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid and "Epiclon 200, 400,
441, 850 or 1050” (Dainippon Ink & Chemicals)
(epoxy resin manufactured by Co., Ltd.), “Epicoat 10.01 or
1004 (epoxy resin manufactured by Siel Kagaku GmbH, Netherlands), “Araldite 6071, 6084” (epoxy resin manufactured by Ciba-Geigy GmbH, West Germany), and “Titsonox 221” (epoxy resin manufactured by Chitso Co., Ltd.) in one molecule. Epoxy group-containing polymerizable adducts obtained by addition reaction with equimolar amounts of polyepoxy compounds having at least two epoxy groups, and low molecular weight polyester resins having polymerizable unsaturated bonds and epoxy groups. Epoxy group-containing polymerizable compounds; hydroxyalkyl (meth)acrylates such as β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate; N-methylolated (meth)acrylates; Acrylamide; or the unsaturated carboxylic acids mentioned above, such as (meth)acrylic acid, maleic acid, fumaric acid or itaconic acid, and "Carduura E" (glycidyl ester of branched fatty acids manufactured by Siel Chemical, Netherlands), octylic acid glycidyl ester or Adducts with monoglycidyl esters of monohydric carboxylic acids such as coconut oil fatty acid glycidyl ester or monoepoxy compounds such as butyl glycidyl ether; Polyester resin, etc. The amount of these vinyl monomers (b) to be used can be determined depending on the amount of the monomer (a) used and the desired coating film performance. For example, gloss,
In order to improve compatibility with nitrified cotton and solubility in solvents, the above aromatic vinyl compounds may be used, and in order to improve gasoline resistance, monomers containing hydroxyl groups as described above may be used. Furthermore, in order to improve adhesion to the material to be coated, monomers having functionalities such as carboxyl groups, epoxy groups and/or phosphoric acid groups in addition to hydroxyl groups are added to the alkyd. In order to improve compatibility, a small amount of nitrogen-containing monomers such as the aforementioned low molecular weight polyester resins and (meth)acrylamides may be used to improve the final target paint, especially for lacquer applications. The ratio of these monomers (a) and (b) to be used may be determined in accordance with the resin composition, required coating film performance, material of the object to be coated, etc. In order to obtain the copolymer constituting the composition of the present invention, using the vinyl monomers listed above,
It can be carried out by a known and commonly used method, for example, a solution polymerization method using a radical generator. Any radical generator that is commonly used in the polymerization of acrylic monomers can be used, but typical examples include azobisisobutyronitrile (AIBN) and di-
such as t-butyl peroxide (DTBPO), benzoyl peroxide (BPO), t-butyl perbenzoate (TBPB), t-butyl peroctoate (TBPO) or cumene hydroperoxide (CHP), and as a solvent. is an aromatic hydrocarbon such as toluene or xylene; acetate esters such as ethyl acetate, butyl acetate or cellosolve acetate; ketones such as methyl ethyl ketone or methyl isobutyl ketone; n-
Typical examples include alcohols such as butanol, i-butanol, and methyl cellosolve. In addition, if necessary, mercaptans, α-
Conventional chain transfer agents such as methylstyrene or "Dipentene-T" (manufactured by Nippon Terpene Chemical Co., Ltd.) can also be used. The copolymer obtained in this way is not particularly limited, but may have a number average molecular weight (n) of
500 to 100,000, preferably 3,000 to 60,000, and the ratio w/n of number average molecular weight (n) to weight average molecular weight (w) is 1.5 to 20. It is said to be the most preferred because it is relatively easy to adjust the balance of physical properties, coating film appearance, texture, coating workability, pigment dispersibility, and solvent release. For the (co)polymer (A) thus obtained,
Lacquer paint is made by mixing a cellulose compound (B) that is poorly soluble or insoluble in water and soluble in organic solvents, or by mixing this cellulose compound (B) with a plasticizer (C). However, if the amount of the (co)polymer used is less than 60%, various properties of the coating film such as solvent resistance, adhesion, and hardness will inevitably deteriorate; If it is used in an excessively large amount exceeding %, it becomes difficult to obtain the effect of adding the above-mentioned cellulose compound (B), etc., which is undesirable. The appropriate amount of the (co)heavy substance (A) to be used is within the range of 60 to 98%, preferably within the range of 65 to 90%. Next, as described above, the cellulose compound (B) is poorly soluble or insoluble in water, and
It refers to compounds that are soluble in organic solvents, and examples of these include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, and nitrified cotton. In particular, various (co)polymers such as those listed above
From the viewpoint of compatibility with (A) etc., it is desirable to use cellulose acetate or nitrified cotton. If the amount of the fiber-based compound (B) used is less than 2%, desired levels in terms of solvent resistance, drying properties, hardness, etc. are likely not to be achieved; If it exceeds 25%, defects tend to appear in terms of slender feel, brittleness, water resistance, weather resistance, etc., which is not preferable. Therefore, the appropriate amount of the cellulose compound (B) to be used is 2 to 25%, preferably 5 to 20%. Furthermore, representative examples of the plasticizer (C) mentioned above include:
Low molecular weight polyesters such as dibutyl phthalate, dioctyl phthalate, butylbenzyl phthalate, dioctyl adipate or acetyltributyl citrate; epoxidized oil systems such as epoxidized soybean oil; or phosphate esters such as tributyl phosphate or tricresyl phosphate are now on the market. (Refer to PP562-563, "7680 Chemical Products," published by Kagaku Kogyo Nippo, January 30, 1980.) However, considering the performance of the resulting coating film, it is difficult to use polyester plasticizers. Most desirable to use. The plasticizer (C) is used to increase the level of flexibility, and if the amount used exceeds 15%, the flexibility will improve, but the solvent resistance will inevitably deteriorate. , stain resistance, weather resistance, etc. are unfavorable.
Therefore, the amount of plasticizer (C) used is 0.
A range of ~15% is appropriate. Besides that,
Resins such as other polyester resins (including oil-modified types), acrylic resins, epoxy resins, or epoxy esters that are compatible with the resin composition for lacquer of the present invention can also be used to prevent splashing and provide weather resistance. For the purpose of improving pigment dispersibility, leveling properties, and pigment dispersibility, conventional paint additives such as antifoaming agents, leveling agents, ultraviolet absorbers, antioxidants, or pigment dispersants may be added in conventional amounts. As the painting method, commonly used methods such as brush painting, spray painting, etc. can be employed. Thus, the compositions of the present invention can be used in automobiles, architectural exteriors,
It can be used in a wide variety of fields such as home appliances, plastics, and interior decoration, but its effects are particularly remarkable in fields where water repellency, stain resistance, and weather resistance are required. Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, all "parts" mean "parts by weight" unless otherwise specified. Example 1 300 parts of toluene,
200 parts of ethyl acetate and methyl isobutyl ketone
200 parts were charged and the temperature was raised to 90°C. At the same temperature 2,
2,3,3,4,4,5,5-octafluoropentyl methacrylate

[Formula] 450 parts, methyl methacrylate 350 parts, n-butyl methacrylate 100 parts, ethyl acrylate 100 parts, toluene
A mixture of 300 parts of AIBN, 5 parts of t-butyl perbenzoate, and 10 parts of t-butyl peroctoate was added dropwise over 5 hours;
Hold for a period of time, non-volatile content 50%, viscosity Z, acid value 0.9,
A resin solution with Mn=19000 and w/n=2.5 was obtained. Example 2 500 parts of toluene and 300 parts of isobutyl acetate were charged into the same four-necked flask as used in Example 1, and the temperature was raised to 115°C. 2, 2, 3, 3, 4, 4,
5,5-octafluoropentyl acrylate
150, 200 parts of methyl methacrylate, 340 parts of ethyl acrylate, 300 parts of n-butyl acrylate, 10 parts of acrylic acid, 200 parts of toluene, 15 parts of AIBN, t
- A mixture consisting of 15 parts of butyl peroctoate and 5 parts of t-butyl perbenzoate was added dropwise at the same temperature over 5 hours and maintained for an additional 15 hours to obtain a non-volatile content of 50%, a viscosity of Z ₂ , an acid value of 4.0, n=28000,
A resin solution with Mw/n=3.1 was obtained. Example 3 500 parts of toluene and 300 parts of isobutyl acetate were charged into the same four-necked flask as used in Example 1, and the temperature was raised to 115°C. Monobutyl mono(3,3,
4,4,5,5,5-heptafluoro-2-pentyl) fumarate

[Formula] 80 parts, 240 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 340 parts of ethyl acrylate, 10 parts of acrylic acid, 200 parts of toluene, 20 parts of AIBN, t-
A mixture consisting of 5 parts of butyl perbenzoate and 10 parts of t-butyl peroctoate was added dropwise at the same temperature over 4 hours, and after the dropwise addition was completed, the same temperature was maintained for about 15 hours to achieve a non-volatile content of 50% and a viscosity of Y, acid value 3.2,
A resin solution with Mn=15000 and w/n=2.1 was obtained. Example 4 Into the same four-necked flask used in Example 1, 500 parts of toluene, 200 parts of methyl isobutyl ketone and 200 parts of isobutyl acetate were charged, and 2,2,
3,3,4,4,5,5-nonafluoropentyl methacrylate

[Formula] 600 parts, β-hydroxypropyl acrylate 10 parts,
200 parts of a total of 1000 parts of a monomer mixture consisting of 280 parts of methyl methacrylate, 100 parts of n-butyl methacrylate, and 10 parts of methacrylic acid, 5 parts of BPO, and 5 parts of t-butyl peroctoade were charged and heated to 90°C. After raising the temperature and keeping it at the same temperature for 1 hour, the temperature was raised to 115℃ over 30 minutes, and the remaining 800 parts of the monomer mixture, 100 parts of toluene, and AIBN20 were heated.
and 10 parts of t-butyl perbenzoate were added dropwise over a period of 5 hours, and the mixture was heated to the same temperature to approx.
Hold for 15 hours, non-volatile content 50%, viscosity Y, acid value 3.3,
A resin solution with Mn=17000 and w/n=2.7 was obtained. Example 5 300 parts of toluene and 300 parts of isobutyl acetate were charged into the same four-necked flask as used in Example 1, and the temperature was raised to 115°C. Then, at the same temperature, N-n-
Butyl perfluorooctane sulfonamide acrylate A mixture consisting of 300 parts of methyl methacrylate, 100 parts of n-butyl methacrylate, 246 parts of styrene, 62 parts of methacrylic acid, 10 parts of AIBN, 20 parts of t-butyl peroctoate, 10 parts of BPO and 200 parts of toluene was added over 4 hours. Immediately after dropping, keep the temperature at the same temperature for 3 hours, then add "Cardilla E" 174
of the liquid was dropped over an hour, and at the end of the drop
EF ₃ - Add 0.1 part of ethyl etherate and maintain at the same temperature for about 15 hours to reduce nonvolatile content to 50%, viscosity Z, and acid value.
4.5, n=22000, w/n=5.9, a resin solution was obtained. Comparative Example 1 Instead of 450 parts of 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate,
The non-volatile content was 50%, the viscosity was Z,
A resin solution with an acid value of 0.9, n=19000, and w/n=2.5 was obtained. Comparative Example 2 A nonvolatile product was prepared in the same manner as in Example 2, except that the same amount of i-butyl acrylate was used instead of 150 parts of 2,2,3,3,4,4,5,5-octafluoropentyl acrylate. A resin solution was obtained with a min of 50%, a viscosity of Z ₁ , an acid value of 3.8, n=28000, and w/=3.1. Comparative Example 3 Monobutyl mono(3,3,4,4,5,5,
5-heptafluoro-2-pentyl) fumarate
The same procedure as in Example 3 was carried out except that the same amount of dibutyl fumarate was used instead of 80 parts, non-volatile content 50%, viscosity W-X, acid value 3.2, n=1500, w/n=
A resin solution of 2.1 was obtained. Comparative Example 4 Instead of 600 parts of 2,2,3,3,4,4,5,5,5-nonafluoropentyl methacrylate,
The same procedure as in Example 4 was carried out except that the same amount of 2-ethylhexyl methacrylate was used, non-volatile content 50%, viscosity X-Y, acid value 3.3, n=17000, w/n=
A resin solution of 2.7 mm was obtained. Comparative Example 5 Example 5 except that the same amount of n-butyl acrylate was used instead of 300 parts of N-n-butyl-perfluorooctane sulfonamide acrylate.
50% non-volatile content, viscosity X-Y, acid value
4.5, n=22000, w/n=5.9, a resin solution was obtained. The various resin solutions obtained in the above Examples and Comparative Examples were made into paints and subjected to physical property tests. The results are summarized in Table 1.

【table】

【table】

【table】

Claims (1)

[Claims] 1 As essential components, (A) 0.01 to 100% by weight of perfluoroalkyl group or fluoroalkyl group-containing vinyl monomer (a-1), and the above monomer (a
-1) and 0 to 99.9% by weight of another copolymerizable vinyl monomer (a-2), which is radically polymerized or copolymerized in the presence of a radical generator. The resulting polymer or copolymer, (B) a cellulose compound that is sparingly soluble or insoluble in water and soluble in organic solvents, and optionally (C) a plasticizer. , resin composition for lacquer.