JPS6021630B2 - Sheet-like material suitable for coating the surface of articles and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sheet-like material that can be thermally hardened at a relatively low temperature and in a short period of time through a radical reaction. The present invention provides a sheet-like material suitable for coating the surface of an article with excellent heat resistance, chemical resistance, oil resistance, corrosion resistance, adhesiveness, etc., and a method for producing the same.

Thermoplastic resins are known as materials for covering the surface of articles, but they have the disadvantage of poor heat resistance and chemical resistance.

In addition, paints such as organic solvent-free water-based, powder-based, high-solids, ultraviolet or electron beam-curable systems have been proposed and used in place of such resins; The formation ability is insufficient and defects such as pinholes are likely to occur, and in aqueous systems there are further problems in wastewater treatment. In hardening type paints,
There are restrictions on the shape of the article to be coated due to the curing conditions, and expensive coating equipment is required. In powder-based paints, thermosetting resins such as epoxy resins and polyester resins are used as the main raw material;
At present, it requires baking at 00qo for 20 to 30 minutes, which limits the material of the article to be coated, and requires expensive coating equipment. On the other hand, as a sheet-type coating material, a type in which resin is formed into a sheet-like film in advance has also been proposed. For example, there is a film formed by mixing an epoxy resin and a curing agent. However, the actual situation is that the adjustment of curing speed and storage stability of lever-based products has not yet been put to practical use.
In other words, if a curing agent with a slow reaction rate is used to prolong the shelf life, the shelf life is good, but it takes, for example, 15 ml to cure.
Heating at 0° C. for 2 to 3 hours is required, and therefore there is a risk of thermal deterioration of the article to be coated, and on the other hand, if a curing agent with a fast reaction rate is used, the storage stability is poor. As a means to solve such problems of curing speed and storage stability, the curing agent is encapsulated in capsules, or the epoxy resin and the curing agent are layered with a diaphragm interposed between them so that they do not react at room temperature. One possible method is to melt or rupture the capsule or diaphragm by applying heat and pressure to start the reaction, but in the case of capsules, it is difficult to select a material for the diaphragm that satisfies both curing speed and storage stability. However, in the case of a diaphragm, the epoxy resin and curing agent are difficult to mix uniformly, resulting in uneven curing. Therefore, the object of the present invention is to provide at least 3
A sheet form suitable for coating the surface of an article, which has a novel heterogeneous structural form that can be stored for several months, hardens very slowly at a heating temperature of at least 100q0, and takes less than one minute to harden. The purpose is to provide materials.

Another object of the present invention is to provide a powder containing a radically reactive unsaturated compound that is solid at room temperature and has a particularly long shelf life as described above and has the property of rapid curing. An object of the present invention is to provide a sheet-like material suitable for coating the surface of an article, which contains a powder containing a radical reaction initiator.

Another object of the present invention is to provide a new method for producing a sheet-like material suitable for coating the surface of an article having the properties described above.

That is, the present invention comprises a powder containing a radically reactive unsaturated compound that is solid at room temperature and a radical reaction initiator that is solid at normal temperature in a self-supporting continuous layer made of a thermoplastic and/or rubbery material. A sheet-like material suitable for coating the surface of an article, which can be cured by heating at a relatively low temperature and for a short time, and is characterized by being dispersed and held in the form of solid particles without substantial contact with the powder containing the The present invention also relates to a suitable method for manufacturing sheet-like materials having such a specific dispersion form.

The sheet material suitable for coating the surface of the article of the present invention (hereinafter referred to as sheet material) is generally in substantial contact with a thermoplastic and/or rubbery material component that can be formed into a continuous layer by heat melting or heat molding. Initiation of a radical reaction between a powder containing a radically reactive unsaturated compound (hereinafter referred to as an unsaturated compound) that is solid at room temperature as a component that exists in a tightly associated state in the form of particles without causing any It is provided as a sheet material with a thickness of about 10 or more, preferably 50 to 500, consisting of a powder component including a powder containing an initiator (hereinafter referred to as an initiator), and has an excellent shelf life, relatively low temperature, and It has the property of being able to harden in a short time and has no defects such as pinholes, making it a suitable coating material.

The thermoplastic and/or rubbery material component used in this invention is a component that serves as the base of a continuous layer in which particles containing an unsaturated compound and particles containing an initiator are dispersed and held in a tightly associated state in the form of particles. , polyvinyl acetate, echele-vinyl acetate copolymer, polyvinyl butyral, polyvinyl acetal, polyamide, ethylene vinyl acetate, alcohol, which is non-reactive with unsaturated compounds or initiators during and after mixing with each of the particles. - soluble nylon,
Saturated polyester, epoxy, phenoxy, acrylic,
Softening point of terbenphenol, petroleum resin, etc. 180q
Thermoplastic resins having a softening point of 80 to 110°C, preferably below the decomposition temperature of the radical initiator, or prebolimers or oligomers thereof are preferably used, such as natural rubber, nitrile rubber, styrene-butadiene rubber, Rubbery materials such as inflation rubber, polychloroprene rubber, evichlorohydrin rubber, butadiene-acrylonitrile copolymer rubber, or prepolymers thereof can be used as well.

Next, the unsaturated compound used in this invention will be explained.

Generally, unsaturated polymers Z (including oligomers) and unsaturated monomers are known as unsaturated compounds.
The unsaturated compound used in this invention is an unsaturated polymer having two or more double bonds in at least one molecule, a mixture of the polymer and an unsaturated monomer, or a mixture of the polymer and an unsaturated monomer having two or more double bonds in one molecule. A mixture with an unsaturated polymer having one double bond is preferable because a cured coating having a three-dimensional molecular structure can be obtained by heating the sheet-like material obtained by the present invention and causing a radical reaction.

In addition, when the unsaturated compound is used alone or in combination as described above, the double bond content is 1 to 9 or more, preferably 1 to 8 × 1 or more. In this case, the number of double bonds belonging to the unsaturated compound having two or more double bonds varies depending on the intended use of the sheet material, but is usually 0.1% or more, preferably 1
．． It is preferably 0% or more, and practically 10% to 100%.

To produce the sheet-like material of this invention, the above-mentioned steps are taken. If the unsaturated compound is solid at room temperature, it is usually left as is; if it is liquid, an additive that is solid at room temperature is added to make it solid at room temperature, and it is added to the thermoplastic and/or rubber material component. It is produced by thoroughly dispersing and maintaining the initiator particles together with the initiator particles so that they are tightly assembled in the form of solid particles without substantially contacting each other, and then forming the particles into a sheet. be done.

The self-supporting sheet-like material of the present invention produced in this way has a thin and substantially continuous layer of thermoplastic and/or rubbery material between the unsaturated compound-containing particles and the initiator-containing particles. Because the particles are interposed as partition walls in a layered state, and both particles are dispersed and maintained in the form of solid particles without substantially contacting each other, the particles remain at a temperature of 25°C for at least 3 months.
It has a shelf life of at least 1 month or more at a temperature of 3500℃ and has a shelf life of at least 100qo when used.
1 minute or less at a heating temperature of at least 800℃
By heating or heating and pressurizing at a relatively low temperature of 0 for 3 minutes or less, the unsaturated compound and the initiator are suitably melted and mixed to cause a radical reaction, resulting in a polymerization reaction, a crosslinking reaction, etc. This reaction forms a cured coating that has a three-dimensional molecular structure and strong adhesion to the surface of the article.

The unsaturated compound used in this invention has a general formula with a molecular weight of about 5,000 or less and has (meth)acrylic acid groups at both ends of the molecule (X is a hydrogen atom or a methyl group, Y is a polyester, polyurethane, epoxy compound, and polyglycol). Advantageously, acrylic unsaturated polymers can be used.

Such an acrylic unsaturated polymer is a compound having a methacrylic acid group or an acrylic acid group at the end of the molecule, and examples of commercially available products include products manufactured by Toagosei Kagaku Kogyo KK that have polyester built into the main chain of the molecule. Oligoacrylate TO-1, TO-3, TO-4, ND-1
, ND-2, product name Oligoacrylate ND-3 manufactured by Toagosei Kagaku Kogyo KK, which contains polyurethane in the molecular main chain, and product name manufactured by Showa Kobunshi Co., Ltd., which contains an epoxy compound in the molecular main chain. Lipoxy RT-802
, VR90×, VR80×, VR60× Product name Lightestel BP-14 manufactured by Kyoeisha Yushi Kagaku Tei, Product name NK Estel 4G manufactured by Shin-Nakamura Chemical Co., Ltd., which contains polyglycol in the molecular main chain, Ship, Momme, P - Examples include books.

Also, the product name Aronix M-55 manufactured by Toagosei Chemical Industry Co., Ltd.
00, M-5700, M-6100, M-6300, M
Acrylic unsaturated polymers such as -8030, M-8060, and IJ Poxy F-900, 840 manufactured by Showa Kobunshi Co., Ltd. can also be used as the unsaturated compound in this invention.

0.1 to 1 of the acrylic unsaturated polymer used at this time
It is also possible to mix unsaturated monomers in a range of 0% by weight, preferably 1 to 3% by weight, and use them as unsaturated compounds in this invention.

Such unsaturated monomers include allylic monomers such as triallyl cyanurate, tolylene diaryl carbamate, diallysocyanurate, N-methylol acrylamide, acrylamide, diacetone acrylamide, triacryl formal, and acrylic. Acrylic monomers such as ethyl acrylate and butyl acrylate,
Examples include vinyl monomers such as vinyl stearate, N-vinylcarbazole, divinylbenzene, and divinyl ethylene glycol, and unsaturated monomers such as maleimide, dimethyl itaconate, and acenaphthylene.

As other examples of unsaturated polymers, conventional unsaturated polyester resins can also be used as unsaturated compounds in this invention.

The above-mentioned polyester resin necessarily contains an unsaturated carboxylic acid such as maleic anhydride or fumaric acid as a component, and a polyester resin obtained by using this together with a saturated polycarboxylic acid and esterifying it with a polyhydric alcohol. These are saturated polymers, and specific examples include Nitto Denko Kaze Nitron V-280, 290, 135, 553, 580 (but does not contain styrene), Toyobo Shohada product names: Upica GLC-316, Yama C- Examples include 234CLS-834, Showa Kobunshi Rigorac-2260, 2030, and 16 spots.

Examples of other unsaturated polyester resins include Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name Eporak P-982Y, G
Examples include -600P and G-18 dirt. Further, in the present invention, unsaturated polymers such as diallylphthalate prepolymers as polymer precursors can also be used as the unsaturated compounds of the present invention.

These unsaturated polyester resins or diallyl phthalate prepolymers can be used alone or in combination with the unsaturated monomers.

The monomer monomers in this case represent from 0.1 to 10% by weight, preferably from 1 to 3% by weight. An unsaturated monomer having two or more double bonds can be used alone as an unsaturated compound in the present invention.

It is also possible to use an acrylic unsaturated polymer and an unsaturated polyester resin in combination. Examples of the initiator used in this invention include dialkyl peroxides such as ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl/gu oxide, diacyl peroxides such as benzoyl peroxide and acetyl peroxide, Hydroperoxides such as tertiary butyl hydroperoxide, cumene hydroperoxide, ketone peroxides such as methyl ethyl ketone hydroperoxide, peracids such as peroxyacetic acid, peroxybenzoic acid, tertiary butyl peroxybenzoate ,
Peroxy esters such as tertiary butyl peracetate, peroxide radical initiators such as peroxycarbonate and peroxyoxalate, or azo radical initiators such as azobisisobutyronitrile and azobisisobutyronitrile, or Examples include inorganic radical initiators such as potassium persulfate and ammonium persulfate.

The amount of the initiator used per unit area of the sheet material is 0.1 to 100, preferably 1 to 100, in terms of the number of active radicals generated from the initiator per 100 double bonds. It is 5 to 50 pieces.

If the radical activity number is less than 0.1, the reaction rate may become slow, and if it is more than 0, this is undesirable because it causes a decrease in the mechanical strength of the cured coating and a decrease in adhesive strength to the surface of the article. In the sheet-like material of the present invention, a thermoplastic and/or rubbery material component is interposed as a partition wall in a thin and substantially continuous layer between particles containing an unsaturated compound and particles containing an initiator. It has a heterogeneous structure in which both particles are dispersed and held in the form of particles without coming into contact with each other, and is characterized by flexibility and flexibility.

The unsaturated compound or initiator is dispersed and retained in the form of particles without substantial contact within the substantially continuous layer barrier structure constituted by the thermoplastic and/or rubber material component. Therefore, the compound or initiator is used in a solid form that retains the form of particles at room temperature (25° C.).

Therefore, if the unsaturated compound or initiator is solid at room temperature, it can be used as is, but if it is liquid at room temperature, an additive that is solid at room temperature may be added to the unsaturated compound or initiator. It is necessary to attach and/or adsorb the agent, disperse or coat it, and maintain it in a solid state at room temperature before use.

Such additives include, for example, unsaturated compounds or initiators that are solid at room temperature (usually 10 to 200 parts by weight per 100 parts by weight of liquid unsaturated compounds or initiators);
Porous powders such as calcium carbonate, barium sulfate,
Titanium dioxide, aluminum hydroxide, clay, talc, asbestos powder, fiber powder (preferably average particle size of about 30 French or less)
or the like, or the thermoplastic and/or rubbery materials which are non-reactive when mixed with unsaturated compounds or initiators and which have a powder-forming structure can be used.

Even when the unsaturated compound or initiator is solid at room temperature, additives capable of forming powder may be added in consideration of storage stability, reaction rate, etc. When an additive is added to an unsaturated compound or an initiator to form a powder, the double bond content in the powder consisting of the unsaturated compound is calculated including the additive, and the number of active radicals of the initiator is calculated. Since the content is calculated including additives, it is sufficient to add an amount sufficient to at least impart powder forming ability within a range that does not deviate from the above-mentioned double bond content and active radical number content. The amount of the additive added is 500% relative to the amount of unsaturated compound used.
% by weight or less, preferably 200% by weight or less, practically 1
0% by weight or less, and 200% by weight for the amount of initiator used.
, preferably 100% by weight or less, and practically 10% by weight or less.

A mixture of an unsaturated compound or an initiator and said additive is
In some cases, powdering aids such as silicic anhydride, aluminum hydroxide, and titanium dioxide, or compounding agents with different functions such as pigments and metal powders are added to reduce the average particle size of the unsaturated compound system in a pulverizer. It is preferable to grind the initiator system to an average particle size of 1 to 30 particles, since this provides good dispersibility and allows for dense association in the form of particles.

Freeze pulverization is used when the material to be pulverized has an arming temperature below room temperature.It is usually deep cooled to a temperature equal to or lower than the embrittlement temperature of the material to be pulverized, and the inside of the pulverizer is brought to an appropriate low temperature. A crushing mechanism that freezes and crushes while being held is a high-speed rotation type impact type. Depending on the structure of the rotor, there are usually three types: hammer mill type, axial flow type, and rotary disc type (pin mill). Although various types of cold soot are known for deep cooling, liquid nitrogen is widely used because it provides an extremely low temperature of -196 qo and is easy to cool rapidly. The sheet material of this invention is
10 parts by weight of said three components, namely a thermoplastic and/or rubbery material component, a particulate component containing an unsaturated compound, and a particulate component including an initiator. In contrast, the particle component (B) is 10 to 100 parts by weight, preferably 50 to 50 parts by weight, and the particle component [B
It is blended and dispersed in a proportion of 1 to 3 parts by weight, preferably 2 to 15 parts by weight.

If the particle component (■) is less than 1 part by weight, the mechanical and thermal strength of the sheet-like material after curing will be poor, and if it is more than 100 parts by weight, the sheet-like material will lack flexibility and have poor conformability to the surface of the article. Furthermore, if the particle component {B} is less than 1 part by weight, the reaction time during curing will be long, and if it is more than 3 parts by weight, the mechanical strength of the sheet material after curing will decrease, the adhesive strength to the article surface will decrease, and pinholes may occur. This is not preferable because it causes defects such as. Therefore, if particle components and additives are added, the above blending ratio is based on the amount without these,
It is necessary to decide.

The characteristics of the sheet material of this invention are the particle components and {
One of the preferred methods for achieving the dispersed form of B', that is, the state where both particles are closely associated in the form of solid particles without substantial contact, is to combine the thermoplastic and/or rubbery material components. It is freeze-pulverized into a powder with an average particle size ranging from 0.1 to 1000 mm, and the above particle components W and tB are added to this powder.
After mixing a predetermined amount of I and forming this powder mixture into a uniform thickness by spraying or painting on a mold release plate baked with mold release synthetic resin such as silicone polymer, pressurize while controlling the heating temperature. It is formed into a sheet in which the particle components and [B] are dispersed and held in the form of solid particles in a self-supporting continuous layer. Another preferred method is to premix the material components and the unsaturated compound, freeze-pulverize this mixture to create a powder mixture with an average particle size of 0.1 to 1000 French, and add the particle components to the powder mixture. A predetermined amount of [B} is mixed and the same operations as above are performed to form a sheet.

In these methods, if the average particle diameter of the material component is less than 0.1 mm, the quality of the particles in the dispersed state is poor, and the thickness of the partition wall between {B} is too thin, making it impossible to obtain good storage stability. This is not preferable because the particle components and the dispersion form of [B} become non-uniform, resulting in variations in the mechanical strength of the cured coating, and the most preferable average particle size is about 5 to 100 μm.

Another method for realizing the particle components and legs in dispersed form is to emulsion the thermoplastic and/or rubbery material components using a solvent such as water or a solvent that does not dissolve the particle components and {B}. , in the form of a slurry or solution, mix a predetermined amount of particle components and {B- with this, mix thoroughly, apply on the mold release slope, and control the heating temperature to disperse water or solvent. There is a method of making a continuous layered sheet by doing this. The sheet-like material of the present invention is constructed as described above, but in some cases, a film or sheet-like base material may be fixed to or interposed between the surfaces of the continuous layers constituting the sheet-like material or between the layers.

The film or sheet material is selected depending on the intended use, and if it is provided on the surface and is intended to function as a surface material, it may be made of metal foil, polyester, polyamide, nylon, polypropylene, etc. When a film or sheet made of resin is interposed between layers to improve the tensile strength of the sheet-like material or to provide other functions such as electrical insulation, a woven fabric made of an inorganic material such as asbestos or glass may be used. or non-woven fabric,
Alternatively, a woven or nonwoven fabric made of an organic material such as the resin described above is selected.

The sheet-like material suitable for coating the surface of an article configured in this way is mainly used for coating interior and exterior seals of electronic parts, anticorrosion lining, etc., but it is also used for electrical insulation purposes of bars and coils of high voltage conductors, The sheet-like material with the film or sheet-like base material interposed therebetween can also be used as a material for laminated molded products.

It is also used for adhesive applications such as adhesion between decorative paper or thin boards and plywood.

In the case of such adhesive applications, since the sheet-like material of the present invention cures at low temperatures and in a short time and exhibits strong adhesive strength, it does not change the amount of water absorbed in the plywood. The fact that the plywood does not warp after being bonded is one of the characteristics exhibited when the sheet-like material of this invention is used for bonding purposes. The sheet material of the present invention can be used in place of conventionally known solvent-based or solvent-free colored paints by adding pigments to the thermoplastic and/or rubbery material components, unsaturated compounds or initiators. Moreover, since it is manufactured as described above, defects such as pinholes are not formed, and a suitable paint-like film can be formed by one-time coating and adhesion. EXAMPLES Next, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples.

Note that "part of the text" means the part by weight. The characteristics of each example are shown in Tables 1, 2 and 3. Example 1 Acrylic unsaturated polymer that is solid at room temperature with a melting point of 70 to 8000 (manufactured by Showa Kobunshi Kaisha, trade name: Ripoxy VR90X)
) into the hopper of the cooling device, deep cooled with liquid nitrogen,
This is freeze-pulverized in a hammer mill set to -100'0 to produce a powder with a 350 mesh pass (average particle size of 10 French or less) and stored at 0°C or below.

On the other hand, a polyester-based saturated polymer (manufactured by Toyobo Fin Shoes Co., Ltd., trade name: ゞ) is used as the matrix of the continuous layer.

#300, softening point 140 to 160 qo) is freeze-pulverized in the same manner as above, classified to produce powder with an average particle size of 5A or less, and stored at 0°C or less. Next, 10 parts of the acrylic unsaturated polymer powder and 100 parts of the above-mentioned saturated polymer powder are mixed at a low temperature of 0° C. or lower, and further 3 parts of penzoyl peroxide are added and sufficiently concentrated.

This powder mixture was spread on a mold release slope on which silicone polymer was baked through a polyethylene resin film on kraft paper so that the thickness after pressurization would be 150 mounds.
9/Ground, temperature 25℃) and gradually warmed to room temperature (25℃) while pressurized.
5 qo) to obtain a self-supporting sheet material. Example 2 10 parts of acrylic unsaturated oligomer (manufactured by Toagosei Kagaku Co., Ltd., trade name Aronix M-8030), 100 parts of powder/talc, silicic anhydride (manufactured by Nippon Aerosil Shoe Co., Ltd., trade name Aerosil R-820) 15 parts and powder. Epoxy resin (manufactured by Shell Chemical Co., Ltd., trade name Epikot 1002) as an additive having forming ability was heated and mixed, and then frozen and crushed in the same manner as in Example 1.
A mixed powder of 350 mesh pass (average particle size of 10 mm or less) is prepared and stored at 0°C or lower.

On the other hand, ethylene-vinyl monoxide copolymer (manufactured by Mitsui Polychemical Tei Co., Ltd., trade name: Bufflex #15, softening point 1200 C) and styrene-butane rubber (manufactured by Nippon Zeon Shoes Co., Ltd., trade name: 1200 C) were used as the matrix for the continuous layer. Famous Ameri Hall 10
11) After heating and mixing with the base part 5, freeze-pulverize in the same manner as in Example 1 to make a powder with 280 mesh passes (average particle diameter of 50 or less), and store it at 0°C or lower. Next, 20 parts of the mixed powder and 100 parts of the base powder were heated to
Below, the mixture is mixed at a low temperature, and 5 parts of penzoyl peroxide is further added and mixed thoroughly.

This powder mixture was heated to a thickness of 20 mm using the same machine as in Example 1.
A sheet material having a self-supporting property of 0.01 is obtained. Example 3 A polyester-based unsaturated polymer that is liquid at room temperature (manufactured by Nippon Shokubai Kagaku Kogyo Tei Co., Ltd., trade name: Eporac G-180) 2 parts, clay 3 base part, 10 parts of glass powder, and an additive having powder-forming ability Non-crosslinked nitrile rubber (as
Nipporu 1072 (trade name, manufactured by Nippon Zeon Vertical Co., Ltd.) was mixed with 10 anchor parts in a kneader, and this was freeze-pulverized in the same manner as in Example 1 to obtain a mixed powder of 280 mesh pass (average particle size of 50 French or less). Prepare and store at below 0°C.

10 parts of this mixed powder and 3 parts of butyl peroxybenzoate (manufactured by Nihon Yushiko Co., Ltd., trade name: Perbutyl Z) are added and mixed at a low temperature with a Henschel mixer.

This powder mixture was pressed onto a glass fiber woven cloth to a thickness of 3.
00 Buddha, and press machine (pressure 10kg/
The material is pressed at a temperature of 3000℃ to obtain a self-supporting sheet-like material.

Example 4 An acrylic unsaturated polymer that is solid at room temperature with a melting point of 70 to 80 qo (manufactured by Showa Kobunshi Hata Co., Ltd., trade name: Lipoxy VR-6 Iso); 10 anchors and polyvinyl butyral as the matrix of the continuous layer (Sekisui Chemical Co., Ltd.); Manufactured by the company, product name: Eslex BLS,
Softening point: 80 qo) 5 anchor parts are heated and mixed with a mixing roll to obtain a mixture.

This was freeze-pulverized in the same manner as in Example 1 to produce a powder with 280 mesh passes (average particle size of 50 peaks or less), and
Save it below.

For every 10 parts of this mixed powder, 4 parts of penzoyl peroxide (trade name: Nyper FF, manufactured by Nippon Yushi Co., Ltd.) is blended and mixed at a low temperature with a Henschel mixer.

Next, 10 parts of this mixture and 20 parts of a polyvinyl acetate solution (solid content 70%) as a matrix for the continuous layer were mixed at a sufficiently low temperature, and this was applied to kraft paper via a polyethylene resin film to form a silicone polymer. The mixture was applied onto a baked release plate so that the thickness after drying would be 200 peaks, and air-dried under reduced pressure (temperature 25 qo) to obtain a self-supporting sheet material.

Example 5 Acrylic unsaturated polymer that is solid at room temperature with a melting point of 40 to 50 qC (manufactured by Showa Kobunshi Tei Co., Ltd., trade name: Lipoxy VR9ho)
A mixture of 100 parts of silicic acid anhydride (manufactured by Nippon Aerosil Tei Co., Ltd., trade name Aerosil R-820) was frozen and ground in the same manner as in Example 1 to obtain 280 mesh passes (average particle size of 50 or less). Make a powder and store it below 000.

On the other hand, an ethylene monovinyl acetate copolymer emulsion (vinyl acetate content: 8% by weight, softening point: 8000, solid content: 55%) was prepared as a matrix for the continuous layer, and 10 parts of this emulsion were prepared. Add anchor and 2 parts of penzoyl peroxide (BPO) and stir thoroughly.

This mixed emulsion was dried on a release plate to a thickness of 10 mm.
Apply to 0A and air dry under reduced pressure (temperature 25qo).
) to obtain a self-supporting sheet material.

Example 6 A polyester-based unsaturated polymer that is solid at room temperature with a melting point of 100 to 11,000 (manufactured by Showa Kobunshi Shoes Co., Ltd., trade name Rigotarac LP-1) was freeze-pulverized in the same manner as in Example 1, and subjected to 300 mesh passes ( A powder having an average particle size of 40 μm or less is obtained.

Next, 50 parts of this finely ground calcium carbonate powder and 3 parts of decanoyl peroxide were blended and uniformly dispersed and mixed using a Henschel mixer. On the other hand, alcohol-soluble nylon (manufactured by Toray KK, trade name CM-4000) as a matrix for the continuous layer was made into a 20% ethanol solution. After the flies have been ground, a glass fiber woven cloth (cheesecloth) is immersed in the mixing bath and adhered for 100 minutes, and then pasted onto a pattern board.

Thereafter, the material is air-dried under reduced pressure (temperature: 25° C.) to obtain a sheet-like material having self-supporting properties. Example 7 Acrylic unsaturated oligomer (manufactured by Toagosei Kagaku Hata Co., Ltd., trade name: Aronix M-8030) 3 Base part, saturated polyester resin (manufactured by Toyo Boseki Hata Co., Ltd., trade name: RV) as an additive with powder forming ability
-100) 10$ aluminum alloy and 1 sparse portion of aluminum hydroxide are mixed in a kneader to obtain a mixture.

This mixture was placed in a hopper of a cooling device, deeply cooled with liquid nitrogen, and then frozen and ground in a hammer mill set at -10 mm, with a particle size of 280 mesh passes (average particle size of 50 peaks or less). A mixed powder consisting of an unsaturated compound having the following properties is prepared and stored at below 0°C.

On the other hand, a saturated polyester resin (manufactured by Toyobo Co., Ltd., trade name: Vylon #3, manufactured by Toyobo Co., Ltd., product name:
0 term softening point 140 to 160° C.) is prepared, and freeze-pulverized in the same manner as above to obtain a single powder having a particle size of 280 mesh pass (average particle size 50 or less).

Next, 50 parts of the single powder and 50 parts of BPOI as an initiator were mixed with 100 parts of the mixed powder at a temperature of ~0°C or less, and the powder mixture was placed on a metal foil on which a silicone polymer was baked. Spray it under reduced pressure below ℃ so that the thickness after forming the sheet is 100 mm, and gradually spread it to room temperature (25 mm).
When the temperature is raised to q0), the single powders recover their self-adhesion to each other, and the powder mixture spread in a layer forms a layered powder mixture without bringing the particles of the acrylic unsaturated oligomer into contact with the particles of the initiator. A self-supporting sheet-like material is obtained which remains dispersed in close association in the form of solid particles.

Table 1 below shows the storage stability of the sheet materials obtained in the above examples in terms of strength at break.

Table 1 (Unit: K Tano IQ) Test method Prepare three specimens each cut into tape pieces with a width of 1 yen and a length of 100 yen.
PM 0x65%R. 3 months under the sun, 1 piece at 40℃ x 65%
R. Day. Below, each piece was stored in a constant temperature room for one month and its strength at break was compared with another piece immediately after manufacture.

This strength measurement method is as follows:
．． Day. The specimen was left in the chamber for 2 hours (the same applies to the stored specimen), and the distance between the chucks was set to 5 mm using a Tensilon tensile strength tester, and the tensile speed was set to 10 cm/mjn (20°C x 65% R).
．． Day. ) was pulled and the value when it broke was determined. 1st
As is clear from the table, the fact that the sheet-like material of the present invention has excellent storage stability is remarkable.

Table 2 below shows the effort adhesion strength and the coating strength of the sheet material at zero strength temperature.

Table 2 Test method Sea bream breaking adhesive strength: A 10 x 1 piece sample was placed between #280 sandplast-finished and degreased 0.8-thick willow aluminum plates and pressurized (pressure 4 [9/ground)]. ),
Heating at the temperature and time shown in Table 2, then 20 pm○×
65%R. Day. The sample was left in a container for 24 hours and measured using a Tensilon tensile strength tester.

Measurement conditions were tensile speed low cape/min, 20qo x 6
5%R. Day. It is. Zero intensity temperature: A sample of 10 x 10 mosquitoes cured by heating at the temperature and time shown in Table 2 was fixed at one end in a hot air circulation dryer and a load of 1M was applied to the other end. The sample was hung vertically in the dryer, the temperature in the dryer was increased at a rate of 2°C per minute, the temperature rose above room temperature, and the temperature at which the sample broke and the load dropped was determined.

As is clear from Table 2, the sheet material of the present invention has excellent deep adhesive strength and coating strength, and also has a fast reaction rate.

Table 3 below shows data showing excellent properties as a coating material for article surfaces, and here shows the results of pencil hardness and pinhole tests.

Table 3 Test method Pencil hardness Conforms to JISK-5400-70.

Pinhole test According to JISG-I92-68, a Holiday detector tester is used to conduct the pinhole test at a voltage of 1200 to 1500V.

The value is expressed as pcs/10x10 arcs. As is clear from Table 3, the sheet material of the present invention is an excellent article surface covering material.

Claims (1)

[Claims] 1. A radical reaction between a powder containing a radically reactive unsaturated compound that is solid at room temperature and a radically reactive unsaturated compound that is solid at room temperature in a self-supporting continuous layer made of thermoplastic and/or rubbery material. A sheet form suitable for coating an article surface that can be cured by heating at a relatively low temperature and for a short time, characterized by being dispersed and held in the form of solid particles without substantial contact with a powder containing an initiator. material. 2 The self-supporting continuous layer has an average particle size of about 0.1 to 1000
A sheet-like material suitable for coating the surface of an article according to claim 1, which is formed from thermoplastic and/or rubbery material powder in the μ range. 3. A sheet-like material suitable for coating the surface of an article according to claim 2, wherein the thermoplastic material powder is a thermoplastic synthetic resin powder having a softening point of 180° C. or lower. 4. A sheet-like material suitable for coating the surface of an article according to claim 1, wherein the self-supporting continuous layer has a film or sheet-like base material fixed to or interposed on the surface or between the layers. 5. Thermoplastic and/or rubbery material powder having an average particle size in the range of about 0.1 to 1000μ, a powder containing a radically reactive unsaturated compound that is solid at room temperature, and a radical reaction initiator that is solid at room temperature. After forming a powder mixture on a mold release plate, the heating temperature is controlled and pressure is applied, and the powder containing the radically reactive compound that is solid at room temperature is mixed in a continuous layer with the powder containing the radically reactive compound that is solid at room temperature. A coating on an article surface characterized in that a powder containing a solid radical reaction initiator is dispersed and held in the form of solid particles without substantial contact with the powder, and is then peeled off from the release plate. A method for producing a sheet-like material suitable for. 6 A mixture of a thermoplastic and/or rubbery material and a radically reactive unsaturated compound is pulverized and has an average particle size of about 0.6 mm.
After forming a powder mixture of a mixed powder of 1 to 1000μ and particles containing a radical reaction initiator that is solid at room temperature on a mold release plate, the heating temperature is controlled and pressure is applied to form a continuous layer. The particles containing the radically reactive compound that are solid at room temperature and the particles containing the radical reaction initiator that are solid at room temperature are dispersed and maintained in the form of solid particles without substantially contacting them, and then A method for producing a sheet-like material suitable for coating an article surface, characterized in that it is peeled off from the release plate.