JPS60104137A - Coating agent - Google Patents

Abstract

PURPOSE:A coating agent having improved adhesivity both to a polyolefin substrate and a top coating agent, providing a uniform composition, comprising a urethane resin of polybutadiene glycol and a chlorinated hydrocarbon resin. CONSTITUTION:(A) A urethane resin obtained from a polyol containing >=50wt% polybutadiene glycol having 500-10,000 average molecular weight, and, if necessary, and other active hydrogen-containing compound components (low-molecular diamine such as aliphatic amine, etc. and <=20wt% based on total active hydrogen-containing compounds), and a polyisocyanate component (e.g., 2-12C aliphatic diisocyanate, etc.), having 5-20wt% urethane bond content, 5,000- 1,000,000mol.wt., and 100-100,000cps/20 deg.C is blended with (B) 3-70wt%, preferably 5-50wt% based on the total amount of both components of chlorinated hydrocarbon resin (e.g., chlorinated PE, chlorinated PP, etc.) having 10-70wt%, preferably 15-45wt% linked chlorine content.

Description

[Detailed description of the invention] The present invention relates to a coating agent.

More specifically, the present invention relates to a coating agent suitable for coating polyolefin molded articles.

Polyolefins such as propylene polymers have the advantages of being inexpensive, lightweight, having excellent solvent resistance, and good processing properties.
Molded products have come to be widely used in automatic t1 (1η-products) and "7JL products 0 cabinets.As a result, painting, adhesion, printing, etc. In recent years, there have been many requests for secondary processing of polyolefins.However, polyolefins have poor polarity, making it difficult for various coating materials to adhere to them.For this reason, chlorinated polyolefins such as chlorinated polypropylene are used in combination with Japanese or other resins. A technique is used to prepare the surface of polyolefin molded products with a solution of
Adhesion to both surfaces and (1) uniformity and properties of the solution were not satisfactory.

As a result of intensive tests a and j, the present inventors have discovered that a composition consisting of a polybutadiene glycol urethane resin and a chlorinated hydrocarbon resin can solve the problem described in -1- above, and have arrived at the present invention. The present invention provides a tacking agent (hereinafter referred to as the present invention) which is secreted into the 'Nlt Bl of a polyolefin molded article made of a polybutadiene glycol urethane resin (a) and a chlorinated hydrocarbon resin (b). (also called coach ink agent).

In the present invention, as the polybutadiene glycol-based urethane resin (a), polybutadiene glycol is usually used in combination with polyol strength'1 having a content J' of 50% by weight or more and, if necessary, other active hydrogen-containing compound components. Examples include resins made of polyisocyanate.

Examples of the polybutadiene glycol include hydroxyl group-terminated polybutadiene oligomers and polymers. Specifically, polyphtadiene glycols include those with a 1,2-vinyl structure, those with a 1,2-vinyl structure and 1,4-1-
those having a lance structure, and 1.4-trans f,
One with 117 structures can be opened. (2) The ratio of the 2-vinyl structure and the 1,4-1-lance structure can be varied, for example, 1oo: 0 to 0: 100 in terms of molarization.
It is. Polybutadiene glycol also includes homopolymers and copolymers (styrene-butadiene copolymer,
acrylonitrile buxene copolymers, etc.).

The average molecule n1 is usually 500 to 10,000, preferably 1,000 to 5,000. Average portion j'11'Cb
; If it is less than 500, the coating agent of the present invention is brittle (
Therefore, the adhesion to polyolefin molded products also decreases.

When the average molecular weight exceeds 10,000, the coating film becomes sticky.

Polybutadiene glycol is specifically deu+,! It is as follows.

C1￥(2C1h C]1271: (5,, waHO 壬(CHr-CH=CH-CHr light(CH-CIl+
ll, -+-TIOHa hill 0.75, b: 0.25, n
Nia 8-87 type (products indicated by 11 are Nl5S
O-1'llG series (to 1 j'!/da products), specifically Ni-1 (100, G-2000 and G-30
00 is opened. The products represented by formulas (2) and (3) include Paly B+I (product of A+<CO, USA), specifically Poly Bd R-45M, R
-451fi'.

Examples include C3-15 and CN-15. The average molecular weight of these products is 1,000 to 50 UOl.14 functional, (number is 1.5 to 25).

For example, as the production d1 of polybutadiene glycol,
A method of converting butadiene into radicals using a catalyst containing a hydroxyl group such as β'-azohis (β-cyano)-1-propanol, a method of reacting butadiene with sodium, lithium, alkylenoxide, epichlorohydrin, etc. 3. Polybutadiene glycol may also be a hydrogenated product thereof (polybutadiene glycol in the present invention also includes hydrogenated products). Hydrogen source JJ
The hydrogen content of polyphtadiene glycol is, for example, between 20% and 100%.1 Hydrogen additives of polyphtadiene glycol are produced using metal catalysts such as nickel, cobalt, platinum, palladium, and ruthenium. Pressure is 10-100
kg/cri), t! can be easily obtained by reacting at 20 to 200°C. Get 1. Hydrogenation may be carried out in the presence of an organic solvent such as hexane, heptano, cyclohexane, etc., if necessary.

In addition to polybutadiene glycol, other polyols such as other high-molecular diols and low-molecular polyols can be used as the polyols, if necessary.

Other polymeric diols include molecular baf, 5 (l O
Examples of polyether siols include mixtures of two or more of the following. ), such as polyethylene-propylene glycol, polyethylene-propylene (Pro, Tsuku d-1 Koha Rank 1\) glycol, polyoxytetramedicylicol, polyoxyhexamethylene glycol, polyethylene-propylene glycol, Oxyoctamethylene glycol, 1;
A mixture of two or more of these may be mentioned. Polyester diol Σ includes dicarboxylic acids (adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid,
phthalate) and glycol l', = r-dylene glycol, propylene glycol, 1llI-methanediol, 1,6-hexanediol, i,8-'cutamethylenethiol, neopentyl glycol, hishydroxymethylcyclohexane, Bishydroxyethylbenzene, alkyl dialkanolamine, rn-xylylene glycol, 14-his(2-hydroxyethoxy)benzene, 44-his(2-hydroxyethoxy)-diphenylbutane/2 and 1 are condensed and polymerized. For example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene/propylene adipate! Polylactone diols, such as polycaprolactone diols; and mixtures of two or more thereof. As polyether ester diols, ether group-containing diols (the above-mentioned polyether diols, diethylene glycol, diethylene glycol, dipropylene glycol, etc.) or mixtures of these and other glycols can be used with the dicarboxylic acids or dicarboxylic anhydrides (phthalic anhydride, etc.) or mixtures of these with other glycols. , maleic anhydride, etc.) and those obtained by reacting with alkylene oxides, such as poly(polyoxytetramethylene) adipate. Average molecule of polymeric diol, lit (hydroxyl group f+lli ill
+1 constant) is usually 500 to 5000, preferably 7
00-4000, particularly preferably 1000-3500
It is.

In addition to high-molecular diols, low-molecular diols can also be used if necessary. As a low molecular diol -
The glycols listed as raw materials for the polyester siols and their alkylene oxide low molar adducts (molecular weight 5
00).

In addition, trifunctional or higher-functional low-molecular-weight polyols can also be used in combination with properties such as ``2''.
Examples of polyols include chrycerin, trimethylolpropane, and pentaerythritol.

Among other polyols, preferred are low-dividing diols [especially ethylene glycol, propylene glycol,
14-butanesilyl, 1/1-his(2-hydroxyethoxy)hensen, 714'-1-su(2-L)
[0-1-jethoxy)-cyphenylbutane] and trifunctional or higher functional low molecular weight polyols (particularly trimethylolpropane).

Other active substances used as necessary (I compounds include low-molecular-weight cyamines, such as fatty 11/J group diamines (ethylenecyamine, 12-brobyleneamine,
hexamethylene diamine, 22.4-1-limethylhexamethylenecyamine), alicyclic J (cyamine (1-amino-3-aminomethyl-3,5,5-l-limethylcyclohexane, 44'- Cyaminorank IJ hexylmethane, isopropylidene dichlormebexyl-/1.4'
-diamines, 14-diaminocyclohexane, etc.), aromatic diamines (xylylenecyamine, 44'-diaminodiphenylmethane, etc.), heterocyclic amines (piperazine, etc.), and mixtures of two or more of these. .

Preferred among these are 44'-diaminodicyclohexylmethane and I-amino-1-aminomethyl-3.5.5-h-limethylcyclohexane.

In the present invention, the content of polyphtadiene glycol in the polyol component is 50 tons or more, preferably 111% or more, preferably 65 tons.
% by weight or more. Polyphtadiene glycol 50
Heavy IN1% end? In the case of l:, :, the uniformity of the solution prepared by dissolving the coach ink agent of the present invention in an organic solvent and the adhesion 191 to the O-polyolefin substrate are low.

The amount of the low molecular weight diol is usually 50 tons, 1% or less, preferably 5 to 30 weight percent, based on the high molecular weight diol containing polybutadiene glycol. The ji of the trifunctional or higher-functional low molecular weight polyol is usually 3 to 11'C% or less, preferably 03 to 2 to 1+%, relative to the polymeric diol containing polyphthadiene glycol.

1t of low molecular weight cyamine is usually 20% by weight or less, preferably (~10%) based on the total active hydrogen content j compound.
Nail 1i1%.

In the polyisocyanate-1 component, the polyisocyanate has a carbon number (NCoJ, (excluding the carbon inside) 2 to
12 aliphatic cyisocyanes-1., alicyclic cyisocyanes-1. having 4 to 15 carbon atoms, Iy2 aromatic aliphatic cyisocyanes-1. having 78 to 12 carbon atoms, aromatic diisocyanes-1. having 96 to 20 carbon atoms, These isocyanane-1.
Modified products of () J-posiimide, urei dione, uretoimino, (content) ornaments, etc.): O, 1, U. Mixtures of these two inserts -1- are listed. 1° Carbon number 2-1
2 aliphatic cyisocyanate-1・includes ethylene diisocyanate-1・, tetramethylene diisocyanate, hexamethylene diisocyanate, dotecamethylene diisocyanate-1・, 22 ll -trimethylhexamethylene diisocyanate-1・, lysine cyisocyanate h; alicyclic cyisocyanate-1 with carbons IJ14 to 18, specifically 14-cyclohexane diisocyane-1, 1-isocyafol 1-l-f isocyanate methyl-3,5,5- h
Limethylcyclohexane (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI),
Methylcyclohexylene diisocyanate (hydrogenated 1”
D I ), isopropylidene dicyclohexyl-44
'-Diisocyane-1.; C8-C12 aromatic aliphatic diisocyanate-1. Also xylylene diisocyanate; Aromatic diisocyane-1. Ne 1-
(TI) I), Cyphenylmethanecyisocyanate
1' (MDI), modified Ml) I (carposiimide modified ('1 etc.), naphthylene shiisocyane-1. is a cycloaliphatic diisocyanate-1, and (
Preferred are hex→)methylene diisocyanate, IPDI and hydrogenated MILr.

Methods for producing the urethane resin (a) include a method in which all the components are polymerized at once (one-shot method) and a method via a prepolymer (prepolymer method), with the prepolymer method being preferred. For example, (1) polyisocyanate
1. Method of reacting a compound and an active f'l hydrogen gold platinum compound so as to have an excess of NCO to form an NCO-terminated prepolymer, and terminating the remaining NCO groups with a reaction terminating agent. 3゜(2) Polyisocyanate The compound and the active r1 hydrogen content j compound are reacted so as to have an excess of NCO, and then further reacted with paper 1' creel or low molecular weight cyamine so as to have an excess of NCO to form an N C: O-terminated prepolymer. After that, there is a method of terminating the reaction by using a reaction terminating agent to remove the remaining Zuro N('0 group).

-1: As the reaction terminator, monoamines (7-alkyl amines such as alcohol + 1-butyramidyl), monoalcohols (ethyl alcohol, 1-fluor alcohol, etc.) or monoamines 11 It is preferred when aliphatic or fatty diisocyanates are used as the polyisocyanate component, and monoalcohols are preferred when aromatic diisocyanates are used.

During the reaction, NCO/active hydrogen-containing groups (OlI, NH
! , N1-1) The ratio is usually 09 to 1,1, preferably substantially 1.

The reaction temperature is usually from 20 to 150''. The reaction is carried out at normal pressure or under elevated pressure. A solvent may be used for the purpose of adjusting the viscosity of the reaction system during the reaction.

Examples of this solvent include aromatic hydrocarbon solvents (such as toluene and xylene), ketone solvents (such as methyl ethyl ketone and methyl isophthyl ketone), and ester solvents (ethyl 1lll'l acid, 11-phthalocyanate, etc.). ,West'
octyl monoacid), cyclic needle solvents (14-dioxyxane, tetrahydrofuran, etc.), formamide solvents (N,N-dimethylformamide, etc.), alcohol solvents (methyl alcohol, ethyl alcohol, isopropyl alcohol, etc.), Multi-alcohol derivatives (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.) and these two
Can be drilled with a mixed solvent.

A catalyst may be used to promote the reaction. As a catalyst, tertiary amines [triethylamine, morpholine, tetramethylquanicine, I-(2-hydroxypropyl) imitasol, N-methyl-N'-hydroxyethylpiperazine, 6> group salts ( lead, hut,
chromium, nickel, octylate or naphthenate of
Dibutyltinmeryl chloride I, cyoctyltine silaure 1, cyphthyldene dimarenii 1, etc.) are available. The use of 1 (%l,
Usually 0.0005 to 3% is preferable based on 1. ,;1
．． o Old) 1-1%.

The amount of urethane resin (a) obtained is +, ! , 1. is usually 5,000 to 1,000,000.

The viscosity is usually 100 to 1 (J0000cps/20"C (
30% melt is 1. The content of polybutadiene glycol in the urethane resin is usually 30 to 85% by weight.

The content of urethane bonds in urethane resin is usually 5 to 2 +
1, il- is the amount %. The terminal end of the urethane resin may be blocked with a reaction terminator or may be an NGO group.

The chlorinated hydrocarbon resin (b) in the present invention includes:
Chlorinated polyethylene, chlorinated polypropylene, chloride com, and their variations 1/1. and mixtures of these two. For example, these chlorinated hydrocarbon resins include polymerizable acrylic compounds (acrylic acid, methacrylic acid, or alkyl esters thereof, etc.) or unsaturated polycarphonic acids (anhydrides) (maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, etc.)
For example, JP-A-57-2812
3, or the chlorinated polyolefin obtained by craft polymerizing the unsaturated polycarphonic acid (anhydride) as described in Japanese Patent Publication No. 5O-HJ916 and Japanese Patent Application Laid-open No. 57-36128. You can open things.

The bonded chlorine content of these chlorinated hydrocarbon resins is usually 1
0-70% by weight, preferably 15-45 tons, lil.

%. If the amount of combined chlorine is less than 10 m + ii%, the coating composition of the present invention will have poor uniformity and properties.
If it exceeds 70 tons/h1%, the weather resistance of the coating film will decrease.

In the coating agent of the present invention, the content 11 of the chlorinated hydrocarbon resin finger (1)) is usually 3 to 70%, preferably 5 to 5%, based on the Orf opening R; 11 of (a) and (1)).
It is 0%. If the content of (1)) is less than 3%, the adhesion to the polyolefin molded article will be insufficient, and if it exceeds 70%, the weather resistance of the coating will decrease.

In the coating agent of the present invention, in addition to the components (fl) and (1) in 1), other solvents may be added as necessary. As the winding machine solvent, the urethane resin (a ) In addition to the same solvents used in the production of
A mixed solvent can be used for the insert. Among these, aromatic hydrocarbon solvents are preferred. In No. 111, the solid content of the coating agent of the present invention is usually 5.
~50 i'((!li%), preferably 10-35% by weight).

The coating agent of the present invention has a dark solvent of 1/1, and other urethane resins, acrylic, melamine, alkyd, etc., which are suitable for improving water resistance, heat resistance, smoothness, etc., of the coating film. Resins commonly used as paint vehicles may be mixed as appropriate. These resins include "Synthetic Resin Coating A'・1-1" (Koubundan Gyokai Co., Ltd., 1939).
December 1 year] (1 shot a month? +'). When mixed, (a) and (b) (7
) Combined d1 fold 1. (Usually 50% or more) - Yu, preferably 6
It should be done so that it becomes 5% or more.

The coating agent of the present invention may also contain additives commonly used in coatings, such as pigments, dispersants, and anti-sagging agents.

The amount is 11. lIJ minute]
-00 weight Ji: Usually 50 tons, 11 meshes, 115 or more, preferably 30 weight parts or less.

The group 4A targeted by the coating agent of the present invention includes:
Polyolefin molded articles (particularly propylene polymer molded articles) are suitable. Others, other plastic molded products,
It can also be used on wood, paper, metal, etc.

The coating agent of the present invention may be applied to the substrate by any conventional method. For example, the coating agent of the present invention may be applied to the target substrate by a coating method such as brushing, spraying, or dipping.3 The coating fii flf usually has a dry film thickness of 5 to 50 μm. After coating, it is usually set at room temperature for 5 to 20 minutes, and then further dried at room temperature or heated. In the case of room temperature drying, it usually takes 3 hours to S E1, and in the case of heating drying, it usually takes 10 to 45 minutes (10 to 45 minutes).It is commonly applied directly to the substrate (one coat).
In addition, it can also be applied wet-on-wet (two or more coats).

The coating film applied and dried in this way usually has 1. Paint is applied. The topcoat may be thermoplastic or thermosetting (eg, commonly used paints such as acrylic, alkyd, urethane thread, epoxy, melamine alkyd, and acrylic urethane). It will be done.

As these coatings F), those described in the above-mentioned [Synthetic wood 11i door/laminating material] can be used.

The coating agent of the present invention has the following effects.

(1) Excellent adhesion to both the polyolefin base material and the 1-coating agent.

(2) A uniform composition can be obtained.

(3) The stability P1 of solution viscosity over time is excellent.

(4) A coating film with good water resistance, solvent resistance, and wood resistance can be obtained.

In addition, the coach ink composition of the present invention has good pigment dispersibility and can produce a coating film with good slipperiness.

The coating agent of the present invention is preferably used as a coating agent for polyurethane resin molded products, particularly propylene polymer molded products, and is also suitably used as an adhesive for these molded products and a vehicle for printing ink.

It can also be used as a coating for other plastics, wood, paper, metal, etc., as an adhesive, and as a vehicle for printing ink.

Hereinafter, the present invention will be explained in detail with reference to Examples and Test Examples, but the present invention is not limited thereto. In addition,
Examples, comparative examples, and test side middle section indicate the 11° C. portion of the nail unless otherwise specified. Each test method and measurement method in the test example is as described in F.

(1) Gloss Regarding the coating surface of each coated board, G (1 - (: 3Hχ
The own foul rate was set at 71jll.

(2) Initial adhesion Regarding the coating film direction of each coated board, J IsK5z. ＋ ＋
A 10 cellophane 11 cellophane tape test was conducted.

(3) Water resistance Each coated board was soaked in 40'C hot water for 240 hours'/2 i'4
After that, the product was left at room temperature for 1 hour, and gloss measurement and rubber 211 IJ Huntave test were performed.

(41 Solvent resistance Each coated plate was coated with n-hexane/n-heptane'/H?M
After soaking in the solvent mixture for 20° (24 hours), the crystals were allowed to stand in a room for 1 hour, and the gloss was measured.
(I conducted an experiment.

(5) Weather resistance Each coated plate was subjected to a lean shine type weatherometer for 1,000 hours in accordance with JIS K5400, and then left at room temperature for 1 hour to measure gloss and perform a Johann 11 Rohan tape test.

Example 1, average content J′ i-,; l 4 (
l old') butadiene glycol (NI SSO P
I3 G-1 (+00, hydroxyl value 72, 4H2O parts,
0.75 parts of trimethylolpropane, 92 parts of ethylene glycol, 8.6 parts of IPI), 0.007 parts of dioctyltin dilaurate, 27 parts of toluene
0i'71! After charging 135 parts of 14-dioxane and 14-dioxane into a 1e Yotsuj-1 Kolben and sealing the system,
Rising to 5°C? ! 1i! ．． After continuing the reaction at this temperature for 8 hours, it was cooled to below 50°C, and 80 parts of isopropyl alcohol, 44-diaminohis(cyclohexyl)
Methane 1.0 i171i Polypropylene toluene 60% molten tt & (Superchron 8 14 H, 11
1 (manufactured by Yokokusaku Valve) ■7.5 t'71≦ was mixed to prepare the coach ink of the present invention. Table 1 shows the appearance of this solution.

Example 2゜Polybutane Junglycol 1, the same as used in Example 1
50 parts, 15 parts of trimethylolpropane, 226 parts of 1,4-bis(2-hydroxyethquine)l, I
I) DI 51.9 parts, dioctyl tin dilaure
1-0,007 parts of toluene, 280 parts of toluene, and 140 parts of 1lI-dioxane were charged into a 114-unit [1 Kolben], and after sealing the system, the system was heated to 90-95°C with PI3, and reacted at this temperature for 10 hours. After that, it was cooled to 50℃ or higher, and 14,211 parts of sea-n-butyl was added.・Cretan+
I got ijl fat melt t1. Add 1 (20%) of this solution to 60% solution of chlorinated polypropylene toluene (Super Chron 8
J, 4H1111 manufactured by Yokokusaku Pulp) were mixed to obtain a coating agent of the present invention. The appearance of this solution is shown in Table 1.

Example 3゜Polybutadiene glycol used in Example 1 and 99.
A urethane resin solution was obtained by carrying out the same operation as in Example 1 using hydrogenated polybutadiene glycol that had been hydrogenated 2%. This solution 100:? 525 parts of a 20% toluene solution of chlorinated polypropylene (Birdren 13-LP, manufactured by Toyo Kasei) was mixed with H to obtain a coating agent of the present invention. Table 1 shows the appearance of this solution.

Example 4 4% by weight was added to 100 parts of the urethane resin solution obtained in Example 1.
20% of chlorinated polypropylene (combined chlorine content: 20 tons, 111%) with maleic anhydride added.
% toluene solution were mixed to obtain a coating agent of the present invention. The appearance of this solution is shown in Table 1.Comparative Example 1゜24 parts of the polybutadiene glycol used in Example 1,
Trimethylolpropane 0.24 ii (, 80 parts ethylene glycol, 1168 parts II"D, 0.007 parts dioctyltin dilaurate, 216 parts toluene and 1
216 parts of 4-dioxane were charged into a 1e 4 x 1 kolben, the system was sealed, and the temperature was raised to 80-85'C.The reaction was continued at this temperature for 6 hours, then cooled to below 50°C. -17.7 parts of n-butylamine was added to obtain a urethane resin solution.To 10 parts of this solution was added 60% of chlorinated polypropylene toluene.
17.5 parts of 14H) were mixed. Table 1 shows the appearance of this solution.
Shown below.

Comparative Example 2 To 100 parts of the (-) urethane resin solution of Example 1, 250 parts of a 60% solution of chlorinated polypropylene toluene (Superchron 814H) was mixed. Table 1 shows the appearance of this solution.
Shown below.

Comparative Example 3 50 parts of toluene was mixed with 100 parts of a 6% solution of chlorinated polypropylene toluene (Superchron 814H). The appearance of this melt is shown in Table 1.

Table 1 Test Example 1 The compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were diluted with toluene so that the solid content was 201l-1lI%, and 10 parts of titanium oxide and carbon were added to 100 parts of these solutions. 0.1 part of Honblack was mixed and kneaded day and night in a hall mill to obtain a test coating solution of 11.j.

A test coating solution whose surface had been degreased with trichloroethane was applied to the two-molded plate by spraying. 5
After drying at room temperature for 7 minutes, dry in a circulating air dryer at 80°.
After drying for 130 minutes (approximately 20 tons between dry films), one layer of each of the thus removed coatings was coated with a commercially available melamine alkyd paint (Flexene 101, one made by Hee Chemical) with thinner ( #101-10) at 2:1 (
After applying by spraying, let it set for 15 minutes at room temperature and dry in a circulating air dryer to 120" C13.
Baking was performed for 0 minutes (dry film distance: approximately 40μ).

thus? (Each test was conducted for each coating.

The test results are shown in Table 2.

Claims (1)

[Claims] ■. Polybutadiene glycol urethane resin (a)
and a coating agent suitable for coating polyolefin molded articles made of chlorinated hydrocarbon resin (l+). 2. (a) is polybutadiene glycol 501Tr1
Claim 1, which is a resin made from an ancient hydrogen-containing compound component consisting of not less than 1'c% of polyols and optionally other active hydrogen-containing compounds, and a polyisocyanate component. Coop ink agent according to item 1. 3. The content of (1)) is (a), t-+ (J (+3
) 0) Coating agent 3° according to claim 1 or 2, which is 3 to 70% based on a ratio of 1:1 to 111.