JPS5830900B2 - Seizouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to paintable rubber products for automobiles and the like.

Similarly, the present invention generally relates to new rubber compositions and methods of making those products.

The state of the art is illustrated in the publications listed below and in the patents listed below.

i.e., U.S. Pat. No. 3,231,634;
No. 362, No. 3.511,792 and No. 3,577,
No. 480, and Enjay Chemical 1 company technical report, EPL-7204 “Vistalon Formu
la 11.401--A New Paintable
Ba5e CompoundJ, and COpO-1y
mer Rubber and Chemica 1 company technical report, “Epsyn BPDM---The pai
ntable BPDM itself”, and Du
Pont's Nordel No. 2903. EPDM
Dupont technical report on the system.

One object of the present invention is a new paintable rubber article with a colored paint coating, the coating being flexible, color stable, and the article having a high flexural modulus and also being elastic. and generally have the property of being able to recover to their initial shape after bending.

Another object of the present invention is to provide a new rubber composition and a method for manufacturing the product. Another object of the invention is to provide a new rubber composition and a method for manufacturing the product, which is more economical from a price point of view. The goal is to provide products.

Another object of the present invention is that the curing rate is fast, thus allowing for more rapid cycle times than were generally possible with previous compositions, i.e. new formulations that are fast but still color stable when applied. Our objective is to provide rubber compositions and products.

Another object of the present invention is to provide new rubber compositions or products whose flow properties are more suitable for molding or extruding the products to be manufactured.

Another object of the present invention is to provide a new system for producing paintable rubber articles that does not require UV surface activation to achieve good paint adhesion.

Other objects, features and advantages of the invention will become apparent from the claims and the following description.

In summary, the present invention provides, by weight, (a) from about 15% to about 90% of a crosslinkable rubber material selected from at least one of the group consisting of styrene-butadiene rubber, polybutadiene rubber, and isoprene rubber; (b) about 0 to about 40% ethylene-propylene diene rubber or neoprene rubber;
, giving the product a high flex modulus and ethylene-ethyl acrylate copolymer, acrylonitrile butadiene styrene, polyvinyl chloride, ethylene vinyl acetate, thermoplastic ethylene-propylene copolymer, acrylic resin,
a thermoplastic polymeric curing agent selected from at least one of the group consisting of cellulose resins and C2-C4 polyolefin polymer materials; (c) 0.01% to about 50% plasticizer; (d) 0 to about 5%; % accelerator, (e) 0.01%
from about 10% curing agent, (f) from 0 to about 10%;
% activator, (g) 0 to about 80% filler material, and a colored paint coating layer on a product made from a flexible color stable paint capable of manipulating the desired color. Become,
This invention relates to a method for manufacturing paintable rubber products for automobiles or the like.

In at least one method aspect, the invention provides that, in weight percent, (a) about 15% to about 90% of at least one of the group consisting of styrene-butadiene rubber, polybutadiene rubber, and isoprene rubber; crosslinkable rubber materials, which also contain less than 50% ethylene-propylene diene monomer rubber or neoprene rubber; (b) from O to about 40%; A thermoplastic polymeric curing agent that provides modulus (
c) 0.01% to about 50% plasticizer; (d) 0 to about 5% accelerator; (e) 0.01% to about 10% curing agent; (f) 0 to about 10%. activator, (g) 0.0
A molded article is formed by formulating a composition comprising 1% to about 80% filler material, molding the composition, and the molding is heated from about 275° F. to about 6000° F. (preferably from 300° F. 4500F) for about 45 minutes to about 14 minutes (preferably 7220 minutes) to prepare a clean surface on the molded product and apply a flexible color stable pigmented paint coating to the product. The present invention relates to a method of manufacturing a novel flexible paintable rubber product with steps.

Crosslinkable rubber materials used in the present invention include styrene-butadiene rubber (5BR), polybutadiene rubber,
and isoprene rubber.

The crosslinkable rubber material may also optionally contain up to 50% ethylene-propylene diene monomer rubber (EPDM) or neoprene rubber.

Preferably, however, the inclusion of this optional EPDM or neoprene rubber in the above-referenced crosslinkable rubber material is kept at less than 15% by weight of the crosslinkable rubber material;
The best results appear to be obtained in the absence of PDM or neoprene rubber.

The amount of crosslinkable rubber material is generally about 15% by weight of the composition.
90% total and preferably about 25% of the composition
% to 60%, and from about 30% to about 5% by weight of the composition.
Best results are obtained in the 5% range.

The thermoplastic polymeric curing agent according to the present invention has been found to impart high flex modulus to the cured composition or the final product formed, and the polymeric curing agent is comprised of ethylene-ethyl acrylate copolymer, acrylonitrile but Jenstyrene, styrene resin, polyvinyl chloride, ethylene vinyl acetate, thermoplastic ethylene-propylene copolymer,
Acrylic resin, cellulose resin, phenolic resin and C
2-C4 polyolefin polymer materials.

The curing agent may also be made at least in part from a C2-C4 polyolefin/acrylic copolymer material.

The amount of this polymeric curing agent present in the composition broadly ranges from 0-40% by weight of the composition, and preferably ranges from about 0.01% to about 40% by weight of the composition. Best results are obtained when the composition is maintained at about 5% to about 20% by weight of the composition.

The plasticizer used in this composition is about 0 by weight of the composition.
．． The plasticizer is present in a wide range from 0.01% to about 50% and is preferably kept in the range from 0.01% to about 35% by weight of the composition, and from about 1% to about 15% by weight. Initial results are obtained using the agent.

This plasticizer is for example Flexon 766 or 5un
thene 410 plasticizer oil, or various other high quality naphthenic oils or various paraffinic materials, or various low molecular weight polyester plasticizers, Petroleum resins and coal tar compounds (coumarone indenes) are likewise used.

Other plasticizers used in the present invention are
US Pat.

The accelerator used in this composition is about 0% of the composition by weight.
It is present in a wide range from about 5% to about 5%, and preferably from about 0 to about 3% by weight, with best results in a range from about 0.01% to about 3%.

Accelerators useful herein are of the type familiar to those skilled in the art, such as cumate, Ultax and various methacrylate monomers (e.g. Sartomer Co
, 5R-206, 297 and 350).

The curing agent used in the composition broadly ranges from about 0.01% to about 10%, and preferably from about 0.5% to about 5%, by weight of the composition. Best results are obtained when kept in the range of about 0.5% to about 3% by weight.

The composition may be sulfur cured or cured with a peroxide curing agent or 5chenectady 5P-
A number of other curing agents may also be used in this composition, such as 1055 curing agents (brominated methylolphenol type, see U.S. Pat. No. 2,972,600), phenol curing agents, quinone curing agents, or amino type curing agents. The activator used may be present in a wide range of from about 0 to about 10% by weight of the composition, and preferably from about 0.01% to about 5% by weight of the composition. Best results are obtained with a range of about 0.1% to about 3%.

The activator may be materials such as zinc oxide, stearic acid, various stearates such as zinc stearate, and various metal halides.

A number of different activators are useful in the present invention and are known to those skilled in the art.

The filler material optionally included in the composition is present in a wide range from about O to 80% by weight of the composition, and preferably at least about O and about 80% by weight of the composition.
Best results are obtained when the filler material is used in the range of about 1% to about 50% by weight of the composition.

Non-pigmenting filler materials may be used, such as carbons, carbon black, carbonate fillers, clays, sulfates, silicas, glass fibers, and other fibrous materials.

Other filler materials will be apparent to those skilled in the art.

The cure compositions discovered and shown in accordance with the present invention are useful for paintable rubber visibility products in the automotive field, various bumper products for motor vehicles, wheel wrap additions, all for passenger cars, injector panels, car lids, trunk lids, It has very satisfactory and advantageous uses such as for and the like.

Numerous other highly useful applications of the present invention may be found where externally applied flexible paintable rubber products are required.

After the composition has been cast and cured as described above, it is generally prepared for painting by applying with either a solvent or detergent wash or other suitable cleaning of the surface.

Generally, the surface to be painted is then suitably activated;
Good paint adhesion is obtained according to the invention.

This surface activation is carried out by halogenation, such as surface chlorination, or by ozone treatment, UV treatment, flame treatment, or electronic treatment.

In some instances, no surface activity is required in some flexible color stable coatings used on cured molding compositions according to the present invention.

In the present invention, ultraviolet treatment of the surface is not necessary and this surface can be prepared to be highly active.
It should be noted that good paint adhesion is obtained by chlorinating the surface to be painted.

It has been found that after the surface has been prepared for painting, generally a paint primer coat should preferably be applied first, although this is optional and not absolutely necessary.

A colored paint coating layer is then applied to the product using a flexible color stable paint coating, for example consisting of a urethane resin coating, an acrylic resin coating, or a polyester resin coating or a combination thereof.

Application of these coatings relies on spraying, brushing, rolling, and similar electrostatic applications.

As pointed out, application of a primer coat is not absolutely necessary.

However, it is generally more economical to use a primer coat because the application of thick colored paint coats that would be required without a primer coat requires the application of thick paint coats with more expensive colored pigment systems.

Similarly, according to the invention it is possible to carry out continuous molding steps, for example by extrusion, and the curing, preparation of the clean surface and application of the color stabilizing paint coating can be carried out continuously in a continuous manufacturing operation. .

Additionally, the product (eg, for filling) can similarly include a textile surface pattern by continuously rolling the textile pattern onto the product after molding and prior to curing.

The advantages of the invention will be apparent from the above description of the invention.

However, it is believed that the following advantages, among others, are obtained with the present invention.

Namely, (1) this new rubber product cures faster;
And thus the molding cycle time is reduced.

(2) This new rubber product is generally more economical because the raw materials used in the invention are obtained at low cost.

(3) Better processability is obtained using this new rubber composition.

(4) Adequate adhesion with topcoat layers is generally readily obtained with this new rubber composition.

(5) With this new rubber composition, the properties of the final product are equal to or better than those of the previous composition.

(6) This new composition provides improved lightfastness of coatings on product substrates.

(7) The rubber composition and method for producing paintable rubber products according to the present invention do not require UV treatment of the surface of the cured rubber composition to achieve good paint adhesion.

(3) Previous compositions based on EPDM rubber:
While these conventional compositions generally have relatively high viscosities that result in undesirable flow properties during molding, the compositions of Rikki's invention have greatly improved flow properties and the compositions and products of the present invention have It is much better suited for molding than previous compositions.

(9) Furthermore, as explained herein, the production of products according to the invention can be carried out in a continuous process.

Examples are presented below to further illustrate the invention.

However, these examples are for illustrative purposes only;
It should be understood that no limitations are intended on the scope of the invention as set forth in the claims.

EXAMPLE 1 While it is clear that the preferred embodiments of the invention as described are well designed to meet the above objects, the invention is susceptible to modifications and changes without departing from the scope of the appended claims. be able to.

Embodiments of the present invention will be shown below.

(1) A patent in which the preparation of a clean surface includes activating the surface to be painted by a surface treatment selected from at least one of the group consisting of halogenation treatment, ozone treatment, ultraviolet treatment, electronic treatment, or flame treatment. The method according to claim 1.

(2) The preparation of the clean surface comprises activating the painted surface by a surface treatment selected from the group consisting of chlorination treatment, ozonation treatment, electronic treatment, or flame treatment. Method described.

(3) The method of item (1) above, wherein the treatment is chlorination.

4. The method of claim 1, wherein the rubber material contains less than 15% ethylene-propylene diene monomer rubber or neoprene rubber.

(5) component (b) is present at about 0.01% to about 25%, component (c) is present at about 0.01% to about 35%, and component (d) is present at about 0 to about 3%; exists, and component (e) is approximately 0
．． 05% to about 5%, component (f) is present from about 0 to about 5%, and component (g) is present from about 0.01% to about 80%. the method of.

(6) The polymeric curing agent is acrylonitrile butadiene styrene, polyvinyl chloride, cellulose resin, styrene resin, phenolic resin, C2-C4 polyolefin polymer material, ethylene ethyl acrylate copolymer, ethylene vinyl acetate. , a thermoplastic ethylene-propylene copolymer, and an acrylic resin, the plasticizer being compatible and non-staining;
A patent that is a non-pigmenting plasticizer and is a substance essentially selected from at least one of the group consisting of naphthenic oils, low molecular weight polyester type plasticizers, petroleum resins, coal tar compound plasticizers, and paraffinic plasticizers. Claim 1
The method described in section.

(7) Claims in which the curing agent is essentially a substance selected from at least one of the group consisting of a sulfur curing agent, a peroxide curing agent, a phenol curing agent, a quinone curing agent, and an amino type curing agent. The method described in Section 1.

(8) The filler is a substance essentially selected from at least one of the group consisting of carbon materials, carbonates, clay sulfates, glass fibers, fibrous substances, and silica. Method.

(9) The polymeric curing agent is acrylonitrile butadiene styrene, polyvinyl chloride, cellulose resin, styrene resin, phenolic resin, C2C4 polyolefin polymer material, ethylene-ethyl acrylate copolymer, ethylene vinyl acetate, The material is substantially selected from at least one of the group consisting of thermoplastic ethylene-propylene copolymers and acrylic resins, and the plasticizer is a compatible non-staining, non-coloring plasticizer. The method according to item (7) above, wherein the substance is substantially selected from at least one of the group consisting of naphthenic oils, low molecular weight polyester plasticizers, petroleum resins, coal tar compound plasticizers, and paraffin plasticizers.

10. The method of claim 2, wherein component (a) is present from about 25% to about 60%.

(11) The method according to claim 6, wherein the colored paint coating layer is selected from at least one resin coating material from the group consisting of urethane resin, acrylic resin, and polyester resin.

(12) Claim 2, wherein the filler material is a material substantially selected from at least one of the group consisting of carbon materials, carbonates, clays, sulfates, glass fibers, fibrous substances, and silica. Method described.

13. The method of claim 7 further comprising comprising an on-product flexible primer paint coating composition below the flexible color stable pigmented paint coating layer.

(14) Claim 11, wherein the filler material is a material substantially selected from at least one of the group consisting of carbon materials, carbonates, clays, sulfates, glass fibers, fibrous materials, and silica. Method described.

15. The method of claim 2, wherein said molding step is carried out by continuously extruding the rubber product.

(16) The method of item (14) above, wherein a textile surface pattern is continuously formed in the product after extrusion and prior to curing.

(17) By weight, (a) about 15% to about 90% of a crosslinkable rubber material selected from at least one of the group consisting of styrene-butadiene rubber, polybutadiene rubber, and isoprene rubber (the rubber material (also contains less than 50% ethylene-propylene diene monomer rubber or neoprene rubber)
(b) 0 to about 40% of a polymeric curing agent that imparts a high flexural modulus to the cure composition; (c) about 0.01% to about 50% of a plasticizer, which is not compatible with A material that is a non-staining, non-staining plasticizer and is selected essentially from at least one of the group consisting of naphthenic oils, low molecular weight polyester type plasticizers, petroleum resins, coal tar compound plasticizers, and paraffinic plasticizers. It is.

), (d) 0 to about 5% accelerator, (e) 0.01% to about 10% curing agent, (f)
(g) from about 0 to about 10% activator; (g) from about 0.01% to about 80% filler material; forming a product by molding the composition; The product is cured at a temperature of about 275°F to about 600°F for a residence time of about 45 minutes to about 14 minutes to prepare a clean surface on the molded article and to provide a flexible color stable coating on the product. A method of manufacturing a flexible paintable rubber product comprising steps of applying a colored paint coating.

18. The method of claim 17, further comprising a flexible primer paint coating composition on the product and below the flexible color stable pigmented paint coating layer.

(19) The method according to item 17, wherein the colored paint coating layer is selected from at least one resin coating material from the group consisting of urethane resin, acrylic resin, and polyester resin.

(20) The method according to item 18, wherein the colored paint coating layer is selected from at least one resin coating material selected from the group consisting of urethane resin, acrylic resin, and polyester resin.

(21) The method of item 17, wherein preparing the clean surface includes treating the surface to be coated with a surface treatment selected from at least one of the group consisting of halogenation treatment, ozone treatment, ultraviolet treatment, electronic treatment, or flame treatment.

(22) The method of item 17, wherein preparing the clean surface comprises activating the surface to be painted by a surface treatment selected from the group consisting of chlorination treatment, ozone treatment, electronic treatment, or flame treatment.

(23) The method of item 21, wherein the treatment is chlorination.

(24) 1 in which the rubber material contains less than 15% ethylene propylene diene monomer rubber or neoprene com;
Method of Section 7.

(25) component (b) is present in about 0 to about 25%;
Component (c) is present at about 0.01% to about 35%, component (d) is present at about 0 to about 3%, and component (e) is present at about 0.01% to about 35%.
05% to about 5%, and component (f) is about 0.01%
present in amounts ranging from about 5% and component (g) being present at about 0.01%
The method of paragraph 17, wherein the method is present in an amount of from about 50% to about 50%.

(26) Component (a) is present at about 30% to about 55%, component (b) is present at about 0 to about 20%, and component (c
) is present at about 1% to about 15% and component (d) is present at about 0.
0.01% to about 3%, component (e) present from about 0.5% to about 3%, and component (f) present from about o.i% to about 3%.
and component (g) is present from about 1% to about 50%.

(27) The method of item 17, wherein the curing agent is essentially a material selected from at least one of the group consisting of a sulfur curing agent, a phenol curing agent, a quinone curing agent, and an amino type curing agent.

(28) The method of paragraph 17, wherein the steps of forming, curing, preparing a clean surface, and applying a color stable paint coating are all carried out in a continuous operation.

Claims (1)

Claims: 1% by weight of: (a) from about 15% to about 90% crosslinkable selected from at least one of the group consisting of styrene-butadiene rubber, polybutadiene rubber, and imprene rubber; (b) a high flex modulus in the cure composition of from about 0.01% to about 40%; (c) about 0.01% to about 50% plasticizer; (d) O to about 5% accelerator; (e) 0.01% to about 10% curing agent. ,(f)
(g) O to about 10% activator; (g) O to about 80% filler; molding the composition; Forming the article by curing at temperature for a residence time of about 20 minutes to about % minutes, preparing a clean surface on the molded product, and applying a flexible color stable pigmented paint coating to the product. A method for manufacturing a flexible paintable rubber product, which is characterized by precautions at each stage.