JPS5945008B2 - Two-part urethane composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a two-part urethane composition useful as a surface coating agent for polyvinyl chloride (PVC).

Although PVC has been used in various fields, it is especially widely used as flooring material because of its good elasticity and water resistance.

However, PVC flooring has the disadvantage that it is sensitive to heat and is easily scorched or abraded by, for example, a cigarette. Therefore, in order to compensate for the drawbacks of pVC, it has chemical resistance and stain resistance. P polyurethane paint with excellent wear resistance and weather resistance
Attempts have been made to paint the VC surface. However,
PVC and general polyurethane have poor adhesion, and even if a general urethane paint is applied to the PVC surface, it will easily peel off. The present inventors conducted various studies in view of the above circumstances and found that a polyurethane paint made of a specific polyester polyol and a specific polyisocyanate has good adhesion to PVC.

That is, in the present invention, the monoaliphatic polybasic acid content is 50 to 10
0% by weight, of which 40 to 100% by weight is adipic acid, and a dihydric alcohol content of 90 to 100% by weight, of which 8 to 30% by weight.
A polyester polyol with a molecular weight of 500 to 5,000 obtained from a polyol component in which
This is a two-component urethane composition for surface coating polyvinyl chloride consisting of a terminal prepolymer. The polyester polyol that is the first component of the composition of the present application has a molecular weight of 500 to 5000, preferably 1000 to 3000,
Those having a hydroxyl value of 30 to 300) preferably 50 to 200 and an acid value of 1 to 20) preferably 1 to 10 are used.

When the molecular weight is less than 500, the composition has water resistance.
Chemical resistance is poor, and if it exceeds 5,000, the viscosity of the polyester polyol itself becomes high, which is unfavorable in terms of workability. The polyester polyol is obtained by reacting a specific acid component with a specific polyol component. The specific acid component is 1. adipic acid alone, 2. a mixture of adipic acid and other aliphatic polybasic acids, 3. a mixture of adipic acid and aromatic polybasic acids, or 4. adipic acid and other aliphatic polybasic acids. or a mixture of aromatic polybasic acids.

In the case of 2 above, the adipic acid is 40% by weight or more, in the case of 3, the adipic acid is 50% by weight or more, and in the case of 4, the aliphatic polybasic acid containing adipic acid is 50% by weight or more, and the aliphatic polybasic acid It is necessary that the content of adipic acid in the resin is 40% by weight or more. The amount of the aliphatic polybasic acid including adipic acid in the acid component is 50 to 100% by weight, preferably 60 to 100% by weight, and when the amount of the aliphatic polybasic acid is less than 50% by weight, the present application When the composition is applied to PVC and cured, the coating film has poor flexibility and poor adhesion to the PVC surface. The amount of adipic acid in the aliphatic polybasic acid is 40 to 100
% by weight, preferably 50-100% by weight. When the adipic acid content is less than 40% by weight, the PV of the composition
Adhesion to C deteriorates. Specific examples of aliphatic polybasic acids other than adipic acid include maleic acid, fumaric acid, succinic acid, sebacic acid, and azelaic acid. Specific examples of aromatic polybasic acids include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and the like. The specific polyol component is 11.4
- It may be a mixture of butylene glycol and other dihydric to tetrahydric alcohols or a mixture of 21,4-butylene glycol, other dihydric to tetrahydric alcohols, and pentahydric or higher alcohols.

In the case of 1, 1,4-butylene glycol is 8 to 30% by weight, and in the case of 2, 2 to 30% by weight contains 1,4-butylene glycol.
It is necessary that the content of tetrahydric alcohol is 90% by weight or more, and the content of 1,4-butylene glycol in the dihydric to tetrahydric alcohol is 8 to 30% by weight.

The amount of di- to tetrahydric alcohol in the polyol component is 9
0 to 100% by weight, preferably 95 to 100% by weight,
When the amount of the di- to tetrahydric alcohol is less than 90% by weight, the viscosity of the polyester resin increases and workability deteriorates. The amount of 1,4-butylene glycol in the dihydric alcohol is 8 to 30% by weight, preferably 10 to 20% by weight.
Weight%.

When the amount of 1,4-butylene glycol in the di- to tetrahydric alcohol is less than 8% by weight, the adhesion between this composition and PVC will be poor, and when it is more than 30% by weight, the composition will not adhere to PVC. When applied to the surface and cured, the abrasion resistance of the coating film becomes poor.

Examples of di- to tetrahydric alcohols other than 1,4-butylene glycol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, 2●4,4-
Trimethyl-1,3-pentanediol, cyclohexanediol, cyclohexanedimethanol, xylylene glycol, hydroquinone bis(hydroxyethyl ether), hydrogenated bisphenol A1 trimethylolethane, trimethylolpropane, trimethylolbutane,
Examples of the alcohol include 1,2,6-hexanetriol, glycerin, tris(hydroxyethyl)isocyanurate, pentaerythritol, and castor oil. Examples of the alcohol having a valence of 5 or more include glycol and shakerose.

The acid component and the polyol component are reacted by a conventional method.

In this case, the 0H/COOH (equivalent ratio) is usually 1 to 2, but it is determined by taking into consideration the raw materials and the molecular weight of the target polyester polyol. Higher fatty acids such as an oil fatty acid, a linseed oil fatty acid, a soybean oil fatty acid, a cottonseed oil fatty acid, a tung oil fatty acid, and a castor oil fatty acid may be blended into the acid component to produce an oil-modified polyester polyol. In this case, the amount of aliphatic polybasic acid in the acid component is used in an amount that does not deviate from the range specified above. The NCO-terminated prepolymer, which is the second component of the composition of the present application, is ω・d-
It is obtained by reacting diisocyanate dimethylcyclohexane with a low molecular weight polyol in an excess of NCO. Examples of ω・d-diisocyanate dimethylcyclohexane include ω・d-diisocyanato-1,2-dimethylcyclohexane, ω・d-diisocyanate-1,3-
Dimethylcyclohexane, ω・d-diisocyanate
1,4-dimethylcyclohexane or a mixture of two or more thereof is used. As a low molecular polyol,
A low-molecular polyol (di- to tetrahydric alcohol, pentahydric or higher alcohol) used in producing the first component polyester polyol is applied. Theoretically, the reaction ratio between ω・d-diisocyanatodimethylcyclohexane and low-molecular polyol is NCO/0H=2, but NCO
By carrying out the reaction at a ratio of /0H>4 and then removing unreacted isocyanate, an NCO-terminated prepolymer with good physical properties can be obtained. The composition of the present invention is a two-component type in which the first component and the second component are stored separately, and when used, they are mixed and applied to PVC.

The NCO/0H ratio between the first component and the second component is 0.2 to 3.
01 is preferably mixed at a ratio of 0.5 to 2.0. A pigment, a leveling agent, a catalyst, etc. may be added to the composition of the present invention, if necessary. The paint thus obtained is coated onto the PVC surface in the usual manner using a bar coater, knife coater, coater, flow coater, spray gun, etc.
It is coated to a thickness of ~300μ, preferably 20-200μ.

PVC coated with the polyurethane of the present invention does not burn in a short time due to cigarette fire, etc., and has excellent stain resistance and abrasion resistance, so it can be advantageously used as a flooring material.

The present invention will be specifically explained below with reference to Examples.

Example 1 200 parts by weight of ω・J-diisocyanate-1,3-dimethylcyclohexane was heated to 80°C with stirring, and 30 parts by weight of 13.25 parts by weight of molten trimethylolpropane was added.
Drips in minutes.

After the dropwise addition was completed, the reaction was continued for 3 hours at 80-85°C.
After the reaction is completed, the reaction mixture is cooled to 35 to 40°C, and while maintaining this temperature, 1 part by weight of benzene and 9 parts by weight of n-hexane are added.
Unreacted ω·d-diisocyanate dimethylcyclohexane is extracted and removed 8 times using parts by weight of the mixed extractant. The amount of extractant is 120 parts for the first time and 100 parts for the second to eighth times.
A small amount of extractant remaining in the extraction residue was completely distilled off, ethyl acetate was added so that the solid content was 75%, the residue was uniformly dissolved, and ω・d-diisocyanate-1・3 with an amine equivalent of 380 was -A dimethylcyclohexane adduct solution was obtained. Example 2 2000 parts by weight of castor oil and 888 parts by weight of phthalic anhydride are mixed, heated to 160° C. while blowing nitrogen, and reacted for 2 hours.

Next, 2000 parts by weight of castor oil, 804 parts by weight of trimethylolpropane, 530 parts by weight of diethylene glycol, 630 parts by weight of 1,4-butylene glycol, and 1752 parts by weight of adipic acid were added, and the mixture was heated for 220 parts by weight while blowing nitrogen gas to remove the condensed water produced. The mixture is heated to ℃ to carry out the esterification reaction. When the distillation of water stops and the acid value becomes 5 or less, heating is stopped and the reaction is terminated.

In this way, a polyester polyol having a molecular weight of about 2,000 to 2,200, an acid value of 4.5, and a hydroxyl value of 136 was obtained. Example 3 4000 parts by weight of castor oil and 295 parts by weight of phthalic anhydride,
1010 parts by weight of sebacic acid was mixed, and the mixture was heated and stirred at 160°C for 2 hours.

Next, 4000 parts by weight of castor oil, 1206 parts by weight of trimethylolpropane, 810 parts by weight of 1,4-butylene glycol, and 1168 parts by weight of adipic acid were added to the reaction mixture, and nitrogen gas was blown in to remove the condensed water produced. An esterification reaction was carried out at 0.degree. C. to obtain a polyester polyol having an acid value of 5, a hydroxyl value of 192, and a molecular weight of about 1900-2100. Example 4 1000 parts by weight of castor oil,
265 parts by weight of diethylene glycol, 315 parts by weight of 1,4-butylene glycol, and 876 parts by weight of adipic acid were mixed and heated to 220° C. while blowing nitrogen gas and removing generated water to perform an esterification reaction.

A polyester polyol having an acid value of 3, a hydroxyl value of 75, and a molecular weight of approximately 2,200 to 2,400 was obtained. Example 5 7300 parts by weight of adipic acid, 200 parts by weight of coconut oil fatty acid, 8000 parts by weight of castor oil, 2700 parts by weight of 1,4-butylene glycol
parts by weight, 150 parts by weight of triethylene glycol, 938 parts by weight of trimethylolpropane, and 2332 parts by weight of diethylene glycol, nitrogen gas was blown into the mixture, and while removing the water produced, the esterification reaction was carried out at 220°C until no water came out. A polyester polyol having an acid value of 4, a hydroxyl value of 145, and a molecular weight of 1,200 to 1,500 was obtained.

Comparative Example 1 200 parts by weight of ω·d-diisocyanate-1,3-dimethylbenzene was heated to 70'C with stirring, and 13.7 parts by weight of molten trimethylolproban was added dropwise over 1 hour.

After the dropwise addition was completed, the reaction was further continued at 65.7°C for 1 hour. The reaction mixture was cooled to 45-50°C, and while maintaining this temperature, unreacted ω・d-diisocyanate dimethylbenzene was extracted in the same manner as in Example 1 using a mixed extractant of 4 parts by weight of benzene and 6 parts by weight of n-hexane. remove. Ethyl acetate was added so that the solid content was 75%, and the residue was uniformly dissolved to obtain a solution of ω.J-diisocyanate-1.3-dimethylbenzene adduct having an amine equivalent of 370. Comparative Example 2 Example 2 except that 540 parts by weight of 630 parts by weight of 1,4-butylene glycol was replaced with 1,3-butylene glycol.
In exactly the same manner as above, the acid value was 4, the hydroxyl value was 136, and the molecular weight was 20.
A polyester polyol of 00 to 2200 was obtained.

Comparative Example 3 5,000 parts by weight of castor oil and 2,072 parts by weight of fluoric anhydride were mixed and heated and stirred at 160° C. for 2 hours.

Next, 1,608 parts by weight of trimethylolpropane, 212 parts by weight of diethylene glycol, 270 parts by weight of 1,4-butylene glycol, and 438 parts by weight of adipic acid were added to the reaction mixture, and the mixture was heated to 220 parts by weight while blowing nitrogen gas to remove water.
C. to perform an esterification reaction to obtain a polyester polyol having an acid value of 5, a hydroxyl value of 170, and a molecular weight of 1,400 to 1,700. Comparative Example 4 268 parts by weight of trimethylolpropane, 848 parts by weight of diethylene glycol, 57 parts by weight of 1,4-butylene glycol
5 parts by weight of adipic acid and 1752 parts by weight of adipic acid were heated and mixed, nitrogen gas was blown into the mixture, and while removing the condensed water produced, 22
The esterification reaction was carried out at 0°C to give an acid value of 5 and a hydroxyl value of 120.
, a polyester polyol having a molecular weight of 1,800 to 2,000 was obtained.

Comparative Example 5 500 parts by weight of castor oil and 148 parts by weight of phthalic anhydride were mixed and heated to 160°C for 1 hour.

Next, 730 parts by weight of adipic acid, 106 parts by weight of diethylene glycol, and 495 parts by weight of 1,4-butylene glycol were added, nitrogen gas was blown in, and while removing the water produced, the mixture was heated to 220°C to perform esterification, resulting in an acid value of 4. ,
A polyester polyol having a hydroxyl value of 85 and a molecular weight of 2,600 to 2,800 was obtained. Example 6 (Painting test) The above isocyanate component and polyol component were mixed so that the ratio of isocyanate groups to hydroxyl groups (NCO/0H) was 1.0.
Add BYK- as a leveling agent.
300 (BYK Mallinckl-0dt) to 0.
2%, 0.01 dibutyltin dilaurate as catalyst
% and mixed until uniform.

After further vacuum degassing, coating was applied to the PVC flooring material using a bar coater so that the dry film thickness was 100 μm.
After forced drying at 0° C. for 20 minutes, it was cured at room temperature for 15 hours, and then a coating test was conducted. Table 1 shows the blending ratio and the results of the coating film test. Wipe it with a damp cloth.

○・・・No abnormality △...Slight traces of ink remain.

×...Ink marks remain.

Momo resistance: According to the taper test method.

Elongation rate: Elongation rate at break of isolated film tensile strength. Tensile strength at break of isolated film

Claims (1)

[Claims] 1 An acid component having an aliphatic polybasic acid content of 50 to 100% by weight, of which 40 to 100% by weight is adipic acid, and an acid component having a dihydric alcohol content of 90 to 100% by weight, of which 40 to 100% by weight is adipic acid. and a polyester polyol having a molecular weight of 500 to 5000 obtained from a polyol component in which 8 to 30% by weight of the polyol component is 1,4-butylene glycol;
2) A two-component urethane composition for surface coating polyvinyl chloride comprising an NCO-terminated prepolymer obtained from ω/ω'-diisocyanatodimethylcyclohexane and a low-molecular polyol.