JPH01129073A - Coating composition - Google Patents

Abstract

PURPOSE:To make it possible to form a coating composition which can be easily applied to various substrates and can give them novel surface appearances and abrasion resistance, scratch resistance, etc., by mixing a polyurethane resin and/or an acrylic rubber with a liquid rubber, a filler and an isocyanate prepolymer at a specified ratio. CONSTITUTION:This coating composition is prepared by mixing film-forming components of 100 pts.wt. polyurethane resin having hydroxyl groups in the molecule and/or an acrylic rubber (A) having hydroxyl groups in the molecule, 1-30 pts.wt. liquid rubber (B) having hydroxyl groups in the molecule, 3-50 pts.wt. inorganic or organic filler (C) and an isocyanate prepolymer (D) in such an amount that 0.8-5.0 equivalents of the isocyanate groups are present per equivalent of the hydroxyl groups of components A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a coating composition, and more specifically, it is a coating composition that can be easily coated on base materials such as metal, plastic, wood, fiber, paper, etc. The purpose of the present invention is to provide a coating composition that imparts a unique surface texture.

BACKGROUND ART Conventionally, various coating agents have been applied to various substrates for corrosion prevention, decoration, and other purposes to improve surface properties.

Particularly in recent years, differentiated coatings have attracted attention, and attempts have been made to impart unique functions to the surface of substrates, and there is a demand for surface treatments that impart functions that are completely different from the texture of the substrate itself. One of these functions is a moist, soft feel, rubber-like elasticity, and non-slip properties.

Conventionally, in order to provide this function, coating the base material with elastic thermoplastic or thermosetting resin such as polyurethane, rubber, soft vinyl chloride resin, silicone resin, etc.
well known.

In general, two-component curing treatment agents made of polyurethane containing hydroxyl groups or acrylic rubber containing hydroxyl groups and incyanate prepolymer have good adhesion to various substrates, cure in a short time at low temperatures, and have excellent wear and scratch resistance. It is also known that a film with good adhesion can be obtained.

Problems to be Solved by the Invention However, when coated with elastic thermoplastic or thermosetting resin such as polyurethane, rubber, soft vinyl chloride resin, silicone resin, etc., there is a problem in soft feel and non-slip properties. However, it has not been possible to simultaneously satisfy both performance and practical functions such as wear resistance and scratch resistance. In addition, in order to satisfy these requirements, there are drawbacks such as requiring high temperature and long processing steps and limiting the types of substrates in terms of adhesion to the substrate.

Also, poly containing hydroxyl groups. When using a two-component curing type treatment agent consisting of urethane or acrylic rubber containing hydroxyl groups and isocyanate prepolymer, a moist texture,
Functions such as slip resistance are inferior to vulcanized rubber, and on the other hand, a two-component curing type treatment agent made of liquid rubber containing hydroxyl groups and incyanate prepolymer provides non-slip properties, but has a moist and It lacks a feeling of squeezing, and has good adhesion to the base material.
It had drawbacks such as poor wear resistance.

An object of the present invention is to eliminate the drawbacks of the above-mentioned conventional methods, and to provide a coating composition that can be easily coated on various substrates and can impart novel surface properties.

Means for Solving the Problems As a result of research, the present inventors found that (A) a polyurethane resin and/or acrylic rubber containing hydroxyl groups in the molecule;
) By combining liquid rubber containing hydroxyl groups in the molecule, (C) inorganic or organic filler, and (D) isocyanate prepolymer in a specific composition, it has good adhesion to various substrates and has excellent softness. We have discovered that it is possible to obtain a coating composition that provides surface properties such as texture and non-slip properties, satisfies various practical performances such as abrasion resistance and scratch resistance, and is easy to process, The present invention has now been completed.

The coating composition of the present invention includes (A) 100 parts by weight of a polyurethane resin and/or acrylic rubber containing hydroxyl groups in the molecule, and (B) 1 to 30 parts by weight of a liquid rubber containing hydroxyl groups in the molecule. Parts by weight, (C) Inorganic or organic filler 3
~50 parts by weight, and (D) isocyanate prepolymer is blended so that the equivalent ratio of isocyanate groups to the hydroxyl groups of component (A) and component (B) is 0.8 to 5.0. Features.

The present invention will be explained in more detail below.

The polyurethane resin containing a hydroxyl group in the molecule in component (A) is obtained by reacting a polyol, an organic diisocyanate, and a chain extender, and has a hydroxyl value of 1 to 50, preferably 10 to 30. things are appropriate. If this hydroxyl value is less than 1, the abrasion resistance and durability of the coating film will be poor, while if it exceeds 50, the drying of the coating film will be slow and workability will be poor, so the hydroxyl value should be set as above. Preferably, the range is .

As the polyol component, those having a molecular weight of 500 to 4000 are used, such as polyethylene glycol adipate, polyethylene propylene glycol adipate, polyethylene butylene glycol adipate, polyethylene glycol adipate, polybutylene glycol adipate, polyethylene glycol succinate,
Polyethylene glycol sebacate, polybutylene glycol sebacate, polytetramethylene ether glycol, poly-ε-caprolactone diol, polyhexamethylene glycol adipate, polycarbonate polyol, polymethylpentenediol adipate, polyglopylene glycol, and the like can be used.

As the organic diisocyanate, 4,4'-diphenylmethane diisocyanate (MD I ), hydrogenated MD
I, isophorone diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate (XDI), hydrogenated XDI, 2.4-)-lylene diisocyanate, 2.6-'tolylene diisocyanate, 1.6 -hexamethylene diisocyanate, 1,
5-naphthalene diisocyanate and the like can be used.

In addition, as a chain extender, ethylene glycol, 1.2-
Propanediol, 1,3-butanediol, neopentyl glycol, 1,4-butanediol, 1,4-butynediol, 1,5-bentanediol, 1,6-hexanediol, 1゜4-bis-(β -hydroxyethyl) terephthalate, 2,2-bis-(4'-β-droxyethoxyphenyl), 1,4-cyclohexanediol, and the like can be used.

On the other hand, as the acrylic rubber containing hydroxyl groups in the molecule, commercially available products having a hydroxyl value of 1 to 20, preferably 3 to 10 can be used. Considering the suitability for various coatings, it is preferable to select and use a relatively low viscosity solution of the acrylic rubber.

As the liquid rubber containing a hydroxyl group in the molecule of component (B), a commercially available product having a hydroxyl value of 3 to 200, preferably 4 to 120 can be used. This liquid rubber is
Examples include 1,4-polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, 1,2-polybutadiene, and isoprene polymer containing hydroxyl groups.

If the molecular weight of these liquid rubbers is small, it will be inferior in terms of imparting a soft feel and slip resistance to the coating film, and if the molecular weight is too large, layer separation will easily occur and the abrasion resistance will be poor.
It is appropriate to use a value in the range of 0 to 30,000.

The inorganic or organic filler of component (C) has a particle size of 0,
1 to 50 is suitable, and as the inorganic filler, precipitated calcium carbonate, light calcium carbonate, heavy calcium carbonate, calcium silicate, clay, synthetic silicate, silicate fine powder, etc. are used. On the other hand, organic fillers include nylon powder, fluororesin powder, polyurethane beads, polyethylene beads, poly10-pyrene beads, polyethylene-vinyl acetate copolymer beads, polysiloxane beads, cross-linked polystyrene beads, cross-linked polymethyl methacrylate beads, and cross-linked benzoguanamine. Resin beads etc. can be used.

If the particle size of these filler particles is less than 0.1,
The tackiness of the surface of the coating film increases, and on the other hand, if it exceeds 5o, the soft feeling of the coating film disappears, so those within the above range are preferred.

Inocyanate prepolymers of component (B) include trimethylolpropane adducts of tolylene diisocyanate (Sumidur L-75: manufactured by Custom Bayer), trimethylolpropane adducts of xylylene diisocyanate (Takenate D-11ON: (manufactured by Takeda Pharmaceutical Co., Ltd.), 1
．． Trimethylolpropane adduct of 6-hexamethylene diisocyanate (Sumidur ■■: manufactured by Sumitomo Ordinance L) 1. Reaction product of 6-hexamethylene diisocyanate and water (Sumidur N-75: manufactured by Ordination Bayer)
It is appropriate to use .

The coating composition of the present invention comprises component (A) 100% as described above.
Based on the weight part, component (B) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, component (C) is 3 to 50 parts by weight, preferably 10 to 30 parts by weight, and component (B) is Ingredients (A
) and the hydroxyl group of component (B), the isocyanate group is blended in an amount of 0.8 to 5.0 (equivalent ratio).

The reason for limiting the mixing ratio of each of the above components is as follows.

If component (B) is less than 1 part by weight, the benefits and non-slip properties that are the object of the present invention cannot be obtained, while if it exceeds 30 parts by weight, the texture becomes sticky, which is not preferable.

Furthermore, if component (C) is less than 3 parts by weight, surface tackiness cannot be eliminated, and if it exceeds 50 parts by weight, it becomes slippery and the desired texture cannot be obtained, which is not preferable.

If the equivalent ratio of the isocyanate group of component (D) to the total amount of hydroxyl groups of component (A) and component (B) is less than 0.8, the abrasion resistance and scratch resistance of the coating film will be reduced. Poor, 5.0
If it exceeds this range, the soft feel and slip resistance will be poor, and the drying properties of the coating film will also be poor, which is not preferable.

The coating composition of the present invention is preferably prepared by the following method. First, a polyurethane resin and/or acrylic rubber containing a hydroxyl group in the molecule of component (A) and a hydroxyl group in the molecule of component (B) are prepared. Next, to this mixture, the inorganic or organic filler of component (C) is added, and after dispersing with a high-speed stirrer or a dispersing machine such as a sand mill, component (D) isocyanate prepolymer is added and mixed. By this method, it is possible to obtain a coating composition that can be applied uniformly and easily to various substrates.

The organic solvent used for preparing this coating composition is as follows:
Examples include ethyl acetate, butyl acetate, methyl isobutyl getone, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, toluene, xylene, and the like.

In addition, the coating composition of the present invention may contain commonly used heavy metal salts or amine salts as catalysts for accelerating curing.1. Alternatively, additives such as antioxidants, ultraviolet absorbers, and light stabilizers may be added as appropriate to further improve weather resistance, and the purpose of the present invention is not impaired by this.

Substrates to which the coating composition of the present invention is applied include, for example, various metals, plastics, wood, fibers, paper, leather,
When applying the coating composition of the present invention to substrates that generally have poor adhesion such as polypropylene and polystyrene, a primer may be used as necessary. may also be used.

As a means for coating a substrate with the coating composition of the present invention,
Known methods such as a spray coating method, a dip coating method, a roll coater method, a reverse coater method, a doctor knife method, and a spacing method can be applied.

When the coating composition of the present invention is applied onto a substrate by the above-mentioned method, it is applied so that the dry film thickness is at least 1.5 cm, and then heated and dried at 50 to 100°C for 5 to 30 minutes. As a result, it is possible to form a coating film that has both a moist and soft texture and is non-slip, and is also excellent in durability.

Example Hereinafter, the present invention will be explained in detail with reference to Examples.

Preparation of hydroxyl group-containing polyurethane solution A 1. 4-Butylene glycol adipate (average molecular weight 2
00G, hydroxyl value 56) 1000 parts, toluene 9
2 parts of toluylene diisocyanate and 157 parts of toluylene diisocyanate were mixed and reacted at 100 to 110°C for 4 hours.
45 parts of butylene glycol was added and the reaction was further continued for 2 hours. After confirming that the isocyanate had disappeared, 902 parts of ethyl acetate was added, and the mixture was cooled to room temperature while stirring.
A transparent polyurethane solution A having a solid content of 40%, a viscosity of 1000 cps/30° C., and a hydroxyl value of 3.7 was obtained.

Preparation of hydroxyl group-containing polyurethane solution B 1. 6-hexamethylene adipate (average molecular weight 200
0, hydroxyl value 56), 1000 parts of toluene, 954 parts of isophorone diisocyanate, and 222 parts of isophorone diisocyanate were mixed.
After reacting at 0 to 110°C for 4 hours, 49.6 parts of ethylene glycol was added, and the reaction was further continued for 2 hours.

After confirming that the isocyanate has disappeared, 954 parts of ethyl acetate is added, and the mixture is cooled to room temperature while stirring, and the solid content is 40%, the viscosity is 250C1)S/30℃, and the hydroxyl value is 10.
．． A transparent polyurethane solution B of No. 5 was obtained.

Preparation of hydroxyl group-containing polyurethane solution C Polytetramethylene glycol (average molecular weight 1000,
Mix 1,125,1000 parts of hydroxyl value, 881 parts of toluene, and 175 parts of water-added xylylene diisocyanate,
The reaction was carried out at 00 to 110°C for 4 hours. After confirming that the isocyanate has disappeared, 881 parts of butyl acetate is added, and the mixture is cooled to room temperature while stirring, resulting in a solid content of 40% and a viscosity of 3.
A transparent polyurethane solution C having a temperature of 50 cps/30° C. and a hydroxyl value of 3.8 was obtained.

Preparation of hydroxyl group-containing acrylic rubber solution Commercially available acrylic rubber solution (product name: XF-1390
, manufactured by Toa Paint Co., Ltd., hydroxyl value 5), was added to a mixed solvent of 640 parts of methyl isobutyl ketone and 160 parts of toluene, and dissolved by stirring for 2 to 3 hours using a high-speed stirrer to obtain a solid content of 20% and a viscosity of 1200 cps/ 30℃
An acrylic rubber solution was obtained.

Preparation of hydroxyl group-containing acrylic rubber solution E Commercially available acrylic rubber solution (trade name: 5P-185,
Toagosei Co., Ltd., hydroxyl value 4) 200 parts were added to a mixed solvent of 640 parts of methyl isobutyl ketone and 160 parts of toluene and dissolved at 100°C, then 4 parts of BPO was added and heated and stirred for about 4 hours while blowing air. After that, it was cooled to obtain an acrylic rubber solution E having a solid content of 20% and a viscosity of 600 cps/30°C.

Example 1 Liquid rubber (
Mix 12 parts of Nikkaso Polybutadiene PBG-2000, manufactured by Nippon Soda Co., Ltd. (hydroxyl value 38), 2 parts of methyl isobutyl keto 22F, and 68 parts of toluene, and add a filler (trade name: Nibseal E-22OA, 11 manufactured by Shiriki Co., Ltd., secondary particle size 1ρ) was added and dispersed for 30 minutes using a high-speed stirrer.Next, before painting this, add isocyanate prepolymer (trade name: Sumidur N-75 Custom Chemical). Co., Ltd.) was added and mixed to prepare a coating composition.

Examples 2 and 3 Coating compositions were prepared in the same manner as in Example 1, except that hydroxyl group-containing polyurethane solutions B and C were used instead of hydroxyl group-containing polyurethane solution A.

Examples 4 and 5 Coating compositions were prepared in the same manner as in Example 1, except that hydroxyl group-containing acrylic rubber solution and E were used in place of hydroxyl group-containing polyurethane solution A. .

Examples 6 to 9 and Comparative Examples 1 to 5 All operations were carried out in the same manner as in Example 1, except that the liquid rubber, filler, and isocyanate prepolymer were changed to those shown in Table 1. A composition for use was prepared.

Experimental Examples Each of the coating compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 5 was applied in an amount of 400 tons to ABS board, hard vinyl chloride board (PVC board), wood board, and paper. /
After spray coating to give nf, it was heated and dried at 60° C. for 20 minutes, and then left at room temperature for 24 hours. Regarding these, various tests shown below were conducted. The result is
It was as shown in Table 1.

However, each test was conducted as shown below.

*1 Each coating composition was applied to various substrates with a dry film thickness of 30a.
After spray coating the film, it was dried by heating at 60°C for 2G, and then dried at room temperature for 24 hours. The samples were subjected to a cellophane tape peel test in the base test.

*2 Each coating composition was coated on an iron plate with a dry film thickness of 30. +1
111 and dried under the above conditions. The dry state of the coating film was examined at room temperature.

*3 The value obtained by dividing the average frictional resistance value by the vertical load when a stainless steel plate with a vertical load of 500 g applied to one sample (dimensions 100 x 200 m) is moved 100 rim at 50 m + / min.

*4 Determine the texture of the *1 sample by touching it with your finger.

*5 *L samples were tested using a Gakushin type fastness tester.
After rubbing 500 times with a load of 200 g using Kanakin cotton cloth, the condition of the painted surface was determined.

*6 Determine the condition of the painted surface after rubbing the sample in *1 with a 100 yen coin.

Evaluation criteria ◎...Excellent○...Good∆...Fair The coating film that is formed has good adhesion to the base material, has a texture that is both moist and soft, and is non-slip, as well as being resistant to palm abrasion. It has excellent scratch resistance and excellent durability. Therefore, the coating composition of the present invention is particularly useful for parts that touch people's hands, such as doors, handles, camera bodies, clothing, printed matter, shoes, bags, etc.
It is useful for application to handbags, telephone receivers, pen holders, containers, etc.

Patent applicant Honey Kasei Co., Ltd. and one other agent
Patent attorney Tsuyoshi Liquidbe

Claims (1)

[Claims] (1) The coating film forming components are (A) 100 parts by weight of polyurethane resin and/or acrylic rubber containing hydroxyl groups in the molecule, (B) 1 to 30 parts by weight of liquid rubber containing hydroxyl groups in the molecule.
parts by weight, (C) 3 to 50 parts by weight of an inorganic or organic filler, and (D) an isocyanate prepolymer in an equivalent ratio of 0.8 to 5 isocyanate groups to the hydroxyl groups of components (A) and (B). .0.0.