JPS5834866A - Composition for urethane coating - Google Patents

Abstract

PURPOSE:To provide a compsn. for urethane coating excellent in weathering resistance, water repellency and soil resistance, prepared by adding an isocyanate compd. to a (per)fluoroalkyl group-contg. vinyl copolymer. CONSTITUTION:(1) 0.01-97wt% vinyl monomer having 1C or higher (per)fluoroalkyl group in which H is substd. with F, and copolymerizable unsatd. double bond, (2) 3-70wt% hydroxyl group-contg. vinyl monomer[e.g., beta-hydroxyethyl (meth)acrylate]and (3) 0-29.99wt% vinyl monomer copolymerizable with (1) and (2) (e.g., styrene) are copolymerized in the presence of a radical forming agent to produce a copolymer which has a number-average molecular weight of 500- 50,000 with it ratio to weight-average molecular weight ranging from 1.5 to 2.0. Then the copolymer and a polyisocyanate compd. (e.g., tolylene diisocyanate) are blended in such an amount that the equivalent ratio between OH and NCO may be 1:0.2-1.5.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new and useful urethane coating composition, and more particularly, it relates to a polyisocyanate compound added to a vinyl copolymer containing a perfluoroalkyl group or a fluoroalkyl group. The present invention relates to a composition that is particularly excellent in weather resistance, water repellency, and stain resistance.

In recent years, acrylic paints have been used in a wide variety of fields due to their outstanding performance, but the required performance is also diverse. -14, the required performance in terms of weather resistance, water repellency, and stain resistance has become even higher, and it is desired that a product that is even more upgraded than the current product be produced.

However, the present inventors have discovered that H4! As a result of intensive research in order to obtain the desired vinyl-based paints, especially acrylic paints with high practical value, we obtained a compound containing a (bar)fluoroalkyl dilute group-containing vinyl monomer as a grinding component. We have completed the present invention by discovering that a polymer can surprisingly improve the various required performances described above5.

That is, the present invention provides perfluoroalkyl group- or fluorotetraalkyl group-containing vinyl monomer (a-1) 1ll
L01~97wt-1 hydroxyl group-containing vinyl monomer (a-2
) 3 to 70 wt-1 and these above monomers (a-1
) and (a-2) and another copolymerizable vinyl monomer (a-2) from 0 to 2,999 weight by weight, with an OH/NCO equivalent ratio of 1/ α2～
The present invention provides a urethane coating composition comprising blending a polyisocyanate compound Qm) in a proportion of 5 to 1/15.

Here, the above vinyl monomer (Hata-1) and 4L
A compound containing a perfluoroalkyl group or a fluoroalkyl group substituted with a fluorine atom and having a longitudinal atom with a prime number of 1 or more, preferably 2 to 18, and a copolymerizable unsaturated double bond. It refers to
In the present invention, any compound having both such a (tsuk-)fluoroalkyl group and an unsaturated bond can be used, but the representative ones are: c(c-)
-COOCHtCFs, CHH=CHCOOCH@CF
zCHFs, CI&= -C(CHs) C00CF
tCHFhC&”CHo 00 CM (,CHJ)
-CtFs, CHs=C(era)eooc,
H(CHs) CsFh CHm= -CHCooC
H(CFi)h C&-C(CHm)COOCH(CF
i) t, CHx=CHCOOCHmCFtCHFCFh
CH! =C(CHI)-COOCH CFICIFCF
hcH,=cncoOCR (mount C)-C, Fy, CH
2=C(CHm)C0OCH(CHs)Cjv,C
OOCHicHz -Cs F1a, C&7C-COO
CH2CM - CH, = Cno c - CHz + CF
! Qi CF@, CHt=CC00CH=CH-COOC mountain CI? , or CsHyOOC-CM Yari CHCOOC
&CtFo etc. These products are produced by reacting fluorinated alcohols with linear, branched or cyclic chains with unsaturated carboxylic acids such as acrylic acid or methacrylic acid or their acid chlorides, or or fluorinated alkanecarboxylic acids with a cyclic chain or their acid chlorides and β-hydroxyethyl (meth)
Acrylate or β-hydroxypropyl (meth)
Reacting with a vinyl monomer containing a hydroxyl group such as acrylate, or reacting an ethylene chlorohydrin adduct of fluorinated ankanesulfonic acid amide with an unsaturated carboxylic acid such as acrylic acid or methacrylic acid, or their acid chloride. It can be obtained by known synthetic methods such as. Of course, these can be used alone or as a mixture of two or more.

And the usage amount of these vinyl monomers (a-1) is [
101 Weight Downwind, abbreviated as -. ), the effect of the monomer cannot be expected, and conversely, if it exceeds α5, the effect of the monomer with the number of teeth can be sufficiently obtained, but the copolymer does not have enough crosslinking points. I can no longer hold it,
This is not preferred because the mechanical properties and solvent resistance of the candle are insufficient (therefore, a range of α1 to 90% is more preferable than α01 to 97-1).

In addition, as the hydroxyl group-containing vinyl monomer (a-2), hydroxyalkyl (meth)acrylate such as β-human fuxyethyl N (meth)acrylate, β-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate is used. ) Acrylates; N-methylolated (meth)acrylamides; unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, fumaric acid or itaconic acid and glycidyl glycidyl, a branched fat plate manufactured by Shell Chemical Co., the Netherlands; Adducts with monoepoxy compounds represented by monoglycidyl esters or butyl glycidyl ethers, such as octyl-glycidyl esters or coconut oil fatty acid glycidyl esters: having a polymerizable unsaturated bond t/ Typical examples include low molecular weight polyester resins, which are important as they provide crosslinking points in the copolymer. If the amount used is less than 3 vI, sufficient transmembrane ability ζ cannot be obtained, and if it exceeds 70 vI, the crosslinking density becomes too high, which is not preferable. Therefore, a range of 10 to 60 −1 is more suitable than 3 to 70 −1. Furthermore, representative monomers that can be used as the vinyl monomer (a-3) include aromatic vinyl compounds such as styrene, vinyltoluene, or α-methylstyrene; methyl (meth)acrylate; Ethyl [meth)acrylate, n-butyl (meth)acrylate or i-
(meth)acrylic acid esters such as butyl (meth)acrylate; diesters of unsaturated dicarbohydrates such as maleic acid, fumaric acid or itaconic acid with alcohols of 11i such as 7#IIIk, C8 to C1l; (meth)acrylamide; (meth)acrylamides such as dimethyl (meth)acrylamide or N-alkoxymethylated (meth)acrylamide; N,N-cyaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate; β-7 Phosphoric acid group-containing (meth)acrylates such as phosphooxy (meth)acrylate; equimolar addition of (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, or a hydroxyl group-containing vinyl monocap and a saturated polycarboxylic acid. Unsaturated carbo(i) groups such as reaction products; glycidyl (meth)acrylate, methylglycidyl (meth)acrylate or (
meth)ol glycidyl ether or unsaturated carboxylic acids such as the above-mentioned (meth)acrylic milk maleic acid and itaconic acid and "Epicron 200.400.44"
．． 1.850 or 1050J (Epoxy Vi#M manufactured by Dainippon Ink Chemical Co., Ltd.), "Epicor" 1001 or 1004J (Epoxy L manufactured by Shell Chemical Co., Ltd. in the Netherlands)
f&), "Araldai) 6071J (epoxy resin manufactured by Ciba Geigy in West Germany), [Chissonox 221
An epoxy group-containing polymerizable adduct obtained by addition reaction with an equimolar amount of a polyepoxy compound having at least two epoxy groups in one molecule, such as J (epoxy resin manufactured by Chisso ■); It is an epoxy group-containing polymerizable compound such as a low molecular weight polyester resin that suppresses unsaturated bonds and epoxy groups, such as "PEOVA" (vinyl ester type manufactured by Shell Chemical Co., Ltd. in the Netherlands), and these vinyl monomers. The amount of (a-3) to be used and the combination thereof may be determined depending on the use of the monomers (a-1) and (a-2) described above and the desired 11!i membrane performance. .

However, among these, phosphoric acid group-containing (meth)acrylates, N,N-dialkylannoalkyl (meth)
Acrylates, unsaturated carbon #! These compounds show a reaction accelerating effect during the curing reaction, and are extremely effective as internal regions, but if used in large quantities, pot life, storage stability, and pigment dispersion stability may be affected. Therefore, for such purposes, the amount of these vinyl monomers used is preferably kept within the range of α05 to 10 −1 (L1 to 5 h).

In order to obtain the copolymer (A) constituting the composition of the present invention, the above-mentioned vinyl monomers are used and a known and commonly used method is used, such as the #wave type method using a radical generator. This can be done by As the radical generator, any of those commonly used in the polymerization of acrylic tertiary polymers can be used, but representative ones include azobisisobutyronitrile (AI).
BN), di-t-butyl peroxide (DTBPO),
Benzoyl peroxide (BPO), t-butyl perbenzoate (TBPB), t-butyl peroctoate (TBPO) or cumene hydroperoxide (C
HP), and the solvents include aromatic hydrocarbons such as toluene or xylene; acetate esters such as ethyl acetate, butyl acetate, or acetic acid solution;
Any ketone such as methyl ethyl ketone or methyl isobutyl ketone that is commonly used in urethane paints can be used as is. Further, if necessary, a conventional chain transfer agent such as mercaptans, α-methylstyrene or [dipentene-TJ (Nippon Terpene Kagaku ■) can be used.

The copolymer (A%-1) obtained by pressing in this way has an average molecular weight (R'i) of 500 to 500, although it is not particularly limited.
5oooo, and this number average molecular weight (M
u) and weight average molecule 1 (□) and <7) ratio My/Ms
It is said that m in the range of 15 to 20 is the most preferable because it is relatively easy to adjust the balance of film physical properties, coating film appearance, texture, coating workability, pigment dispersibility, and solvent release.

On the other hand, typical examples of the polyisocyanate compound as another component constituting the composition of the present invention include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, or xylylene diisocyanate; tetramethylene diisocyanate; Aliphatic diisocyanates such as iso7anate, hexamethylene diisocyanate or trimethylhexane diisocyanate; isophorone diisocyanate, methylcyclohexane-2,4- (not L!-!, 2°6-)
diisocyanate), 4. Alicyclic diisocyanates such as 4'-methylenebis(cyclohexyl isocyanate) or 1,6-di(isocyanatomethyl)-cyclohexane; or each of these diisocyanates and a variety of diisocyanates such as ethylene glycol, propylene glycol, neopentyl glycol or trimethylolpropane. Low molecular weight polyester 11 resin (low molecular weight polyester 11 resin) that has a functional group that reacts with alcohols or isocyanate groups.
It is an adduct with water, etc. (including oil-denatured type),
It is a biuret type, or a polymer (including oligomers) of 3 diisocyanates, and furthermore, polyisocyanates such as those mentioned above are made into blocks using a known and commonly used blocking agent. However, when used outdoors, polyisocyanates other than aromatic diisocyanates, which do not yellow due to ultraviolet rays, or their various derivatives are recommended for the weather resistance of the coating film. It is concluded that it will be used. In particular, commercially available products include "Parnock D-750% DN"
-950, DN-970? ：D-800、"(Dainippon Ink & Chemicals) RFI Kene) B-82ONS
, D-11ON.

D-123N Mataha D-140N (manufactured by Takeda Yakusho ■), Conquanate L, EH or 2031J (manufactured by Nippon Polyurethane ■), Desmodur L, N or HLJ (manufactured by Bayer AG, West Germany), etc. , the blending ratio of these polyisocyanate compounds (4mB) and the copolymer (A) is oVNc.

A range of =110.2 to 1/15 (equivalent ratio) is preferable from the viewpoint of m-group performance. In other words, N for one lid of OH
If the amount of GO is less than 12fi, sufficient coating performance will not be obtained, but if the amount of NCO exceeds 15 equivalents per equivalent of OH, the coating will tend to become brittle and foam. Undesirable.

The composition of the present invention thus obtained can be used as it is as a clear paint, or can be further mixed with #I to be used as an enamel paint. Furthermore, various conventional additives can be added to the composition of the present invention, if necessary. For example, cellulose compounds such as nitrocellulose or cellulose acetate butyrate, plasticizers, or polynisder resins (including oil-modified types) can be used to further improve thinner resistance, dryness, texture, and flexibility. ), other resins such as noacryl IIIt resin, epoxy resin, or epoxy ester may be used within the range that is compatible with the composition of the present invention,
Leveling agent, ultraviolet! ! Coating additives such as absorbents or pigment particulate agents may also be used.

As for the painting method, commonly used methods such as brush painting, spray painting or roll painting can be used, and the curing method can range from room temperature drying to heat drying.
Optimal curing conditions can be designed according to the application or material properties.

Depending on the type of polyisocyanate, the composition of the present invention can be used in a wide variety of fields such as automobiles, home appliances, building exteriors, brace metal, and interior materials. Its effectiveness is remarkable in fields where water resistance, Ii water resistance, and stain resistance are required.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, where "parts" in the text are "parts by weight" unless otherwise specified.
shall mean.

Example 1 200 parts of toluene and 500 parts of isobutyl acetate were charged into a four-way flask equipped with a stirrer, an inert gas inlet, a thermometer, and a condenser, and the temperature was raised to 115°C. At the same temperature, 190 parts of β-hydroxyethyl methacrylate, 150 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, 150 parts of ethyl acrylate, 10 parts of methacrylate, 300 parts of isobutyl acetate, 10 parts of IBN
and 20 parts of t-butyl perbenzoate v was added dropwise over 5 hours and kept for an additional 15 hours until the non-volatile content was 509 g, viscosity IjILz, acid value 5.4, OH
A resin solution with a value of 40 Mn=11000.1 age 46=2.1 was obtained.

Example 2 Same Yotsuro flask K as used in Example 1, toluene 5
00 parts and 5 oostl of isobutyl acetate were charged, and the temperature was raised to 115°C. 2.2.3.5.4.4.5.5
-Octafluoropentyl acrylate 150 parts, β
-Hydroxyethyl methacrylate 1? O8B, 350 parts of methyl methacrylate, amount - butyl methacrylate)
100 parts, ethyl acrylate 100 parts, Otori-butyl acrylate 100 parts, acrylic ##1011. A mixture consisting of 200 parts of vinegar 612 YpFK, 10 parts of AIBNB, 10 parts of t-butyl methacrylate, and 15 parts of t-butyl perbenzoate was added dropwise at the same temperature over 5 hours, and the mixture was kept for about 15 hours. Non-volatile content 50-1
Viscous & Zi~Z, acid value 40, OR value 4゜Mn=1400
Example 3 Toluene 3 was added to the same four-bottle flask as used in Example 1.
00i1S and 500 parts of butyl acetate were charged and 12
The humidity was increased to 0'Ck. Mottuptil Mono (3, 5, 4, 4
,5,5,5-hedroxyethyl methacrylate 26
2 parts, 350 parts of styrene, 18 methyl methacrylate
0 parts, dibutyl fumarate 50 parts, n-butyl acrylate 100 parts, acrylic @ f3 parts, acetic acid 7'f
- A mixture consisting of #200i1S, 10 parts of AIBN, 10 parts of t-butyl perbenzoate, and 5 parts of di-t-butyl peroxide was heated at the same temperature for 4 hours and kept at the same temperature for about 15 hours after finishing the reaction. Non-volatile content 50-1
Viscosity P, acid value &2, OHHSO36 Tsuta 8000, My/
A resin solution with Mn=2.9 was obtained.

Example 4 To the same four-ton flask used in Example 1, 4 toluene was added.
00 parts of isobutyl acetate and 400 parts of isobutyl acetate were added, followed by a monomer consisting of 84 parts of K2.2.5.5.4.4.5.5.5-nonafluoropentylmethacroxyethyl acrylate, 56 parts of methyl methacrylate, and 10 parts of methacrylic acid. 200 parts of 1,000 parts of the total amount of the polymer mixture, 5 parts of BPO, and 7 parts of t-butyl peroctoate were charged, heated to 100°C, held at the same temperature for 30 minutes, and then heated to 100°C for 30 minutes. Then, the temperature was raised to 115°C, and the remaining 800 parts of the monomer mixture and an additional 200 parts of isobutyl acetate were added.
A mixture consisting of 10 parts of N and 8 parts of t-butyl perbenzoate was added dropwise over 4 hours and kept at the same temperature for about 15 hours to give a non-volatile content of 5 aqk and a viscosity of 23.
, acid value 55, O) f value 20, M Otori = 17000, MY/
A resin solution with Mn=5.2 was obtained.

Example 5 Xylene 2
00 parts and butyl acetate 500 parts and heated to 120°C.
The temperature rose to . At the same temperature, perfluorocyclohexyl acrylate (CHt=CH-C00C horse-C, F mouth) 60
0 parts, β-hydroxyethyl acrylate 84 parts, methyl methacrylate) 206 parts, Otori-butyl methacrylate 100 parts, acrylic 1210 parts, butyl acetate
300ii AIBN 20 parts, t-butyl peroctoate 10 parts and di-1-butyl peroxide 1
A mixture consisting of 0 parts was added dropwise over 6 hours and kept at the same temperature for about 10 hours after the addition, until the non-volatile content was 50-1.
Viscosity 2! ,jl! 1ffi4.0, OH*20, Mn-
15,000 and Mw/Mn=55 was obtained.

Example 6 Into the same four-way flask used in Example 1, 2 toluene was added.
00 parts, xylene 100 parts and butyl acetate 500 parts
The temperature was raised to 120°C. Then, at the same temperature, N
-rr-petitaba-fluorooctane sulfonamide acrylate-hydroxyethyl methacrylate-) 461tS,
200 parts of styrene, MethyM Tacryle←) 100i1. i
-Butyl acrylate 1181L methacrylate @ 62
parts, 10 parts of MuIIN, 20 parts of t-butyl peroctoate, 10 parts of IIPo, and 20 parts of butyl acetate.
A mixture consisting of 0 parts of 'Cl1Ii was added over a period of 4 hours, and immediately after the addition was completed, the temperature was maintained at the same temperature.
Add 111 parts of 174 parts of J over t-1 hour (dropping, BF, -ethyl Nieteller at the end of the lowering) and hold for about 15 hours at the same time to obtain a non-volatile content of 50-1 viscosity Y ~ 2° acid A resin solution with a value of 4.6.0 Hfi1, an i-value of 10,000, and a value of 116 and 5 was obtained.

Comparative Example 1 150 parts of h-butyl methacrylate and n-butyl acrylate instead of 2,2.5,5.4.4.5.5-octafluoropentyl methacrylate L/-) 4501S
The same procedure as in Example 1 was carried out except that 300 parts of the non-volatile content was used, the viscosity was
0, Mn = 11,000°, and a resin solution with Mu = 2.1 was obtained.

Comparative Example 2 Same as Example 2 except that in addition to 150 parts of 2,2.5.5.4.4.5.5-octafluoropentyl acrylate, 150 s of lIc1-butyl acrylate was also used. Minutes 50-1 viscosity 22. Acid value 58, -
A resin solution with an OH value of 40, a resistance value of -14,000, and a germination value of 2.4 was obtained.

Comparative Example 3 In addition to 80 parts of motubutyl-mono-(5,3,4,4,5,5,5-hebutafluoro-2-pentyl) male), 80 parts of Sara Kl-butyl acrylate were also used. was prepared in the same manner as in Example 3, with a nonvolatile content of 50% and a viscosity [P~
Q, acid value 52, OHHSO3Mnz8000. Mw7/
A resin solution with Wn=2.9 was obtained.

Comparative Example 4 In addition to 2,2.3.5.4.4.5.5.5-nonafluoropentyl (9-) 85011/), 400 parts of ethyl acrylate and 450 parts of non-butyl acrylate were used. Others were the same as Example 4, non-volatile content 50%, viscosity 2, #Ih3.5, OH*208
, l1ha-17000, My/Mu = 12, a resin solution was obtained.

Comparative Example 5 In the same manner as in Example 6, except that in addition to 30011 g of N-n-butylflurofluoropoctanesulfonate 7-di-IJL'-), 600 parts of ethyl acrylate was also used, the non-volatile content was 501 Jl, the viscosity was X~1', Oxygen 4
4. OH detective so.

A resin solution with Mm=10,000 and My/Mn=5.5 was obtained.

The tree sap from each ridge obtained in the above Examples and Comparative Examples was made into a paint and physical property tests were conducted. The results are summarized in Table 1IE1.

Claims (1)

[Scope of Claims] Perfluoroalkyl group or fluoroalkyl group-containing vinyl monomer (*-1), 0.01 to 97% weight, hydroxyl group-containing vinyl monomer (a-2) 3 to 70% weight and other vinyl monomers (&-5) copolymerizable with the above monomers (a-1') and (a-2)
A composition for a urethane paint, which is obtained by blending a polyisocyanate compound (Shiota) with a copolymer η) obtained from -〇~2999wt~ so that the equivalent ratio of □ii/NGO is 1/α2~1/15. .