JP6590587B2 - Coating materials and articles - Google Patents

Description

  The present invention relates to coating materials and articles.

  Conventionally, silicone coating materials have been used for the purpose of imparting antifouling, water repellency, oil repellency, releasability, heat resistance, weather resistance, scratch resistance, coating slip properties, etc. to various substrate surfaces. Has been studied.

As the silicone-based coating material, a so-called silicone varnish obtained by dissolving a relatively low molecular weight silicone having a crosslinkable group such as a silanol group at an end in an organic solvent is generally used.
Silicone varnish may be used in combination with a crosslinking agent or a curing agent for the purpose of accelerating the crosslinking reaction and lowering the curing time or the curing temperature (for example, Patent Document 1).

International Publication No. 2009/60535 Pamphlet

  According to the study by the present inventors, it has been clarified that a silicone varnish combined with a crosslinking agent or a curing agent may be gelled due to the progress of the crosslinking reaction during storage. A two-component type method in which a crosslinking agent or a curing agent is added and mixed immediately before coating, or a method of curing by ultraviolet irradiation or the like is also conceivable. However, such a method complicates the coating operation.

  The present invention has been made in view of the above circumstances, and is excellent in storage stability and imparts properties (eg, coating slip properties, etc.) expected of a silicone varnish to a substrate by a simple means. A coating material that can be applied is provided.

  That is, according to the present invention, the following coating materials and articles are provided.

（上記式（１）において、Ａ^１、Ａ^２およびＡ^３は各々独立に、ポリオレフィン鎖または炭素数１〜１０の炭化水素基である。Ｒは炭素数１〜１０の炭化水素基である。各Ｒは同一でも異なっていてもよい。ｍは１〜１０，０００の整数である。Ａ^３が複数存在する場合、各Ａ^３は同一でも異なっていてもよい。ただし、Ａ^１、Ａ^２、Ａ^３のうち、少なくとも１つはポリオレフィン鎖を表す。）
［５］
上記コーティング材中の上記シリル化ポリオレフィンの含有量が、上記ポリオレフィン１質量部に対し、０．００５質量部以上９０質量部以下である、上記［１］乃至［４］のいずれか一つに記載のコーティング材。
［６］
上記コーティング材中の上記ポリオレフィンの含有量が、上記有機溶媒１００質量部に対し、０．１質量部以上５５質量部以下である、上記［１］乃至［５］のいずれか一つに記載のコーティング材。
［７］
上記［１］乃至［６］のいずれか一つに記載のコーティング材により形成されたコーティング層を備える物品。 [1]
Including a polyolefin having a melting point of 40 ° C. or higher and 105 ° C. or lower, a silylated polyolefin, and an organic solvent,
A coating material in which the polyolefin and the silylated polyolefin are dissolved or dispersed in the organic solvent.
[2]
The coating material according to the above [1], wherein the polyolefin contains at least one selected from an ethylene / α-olefin copolymer (A1) and a propylene / α-olefin copolymer (A2).
[3]
The coating material according to [2], wherein the propylene / α-olefin copolymer (A2) satisfies the following requirements (i) and (ii).
(I) The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 3,000 to 40,000. (Ii) Propylene origin in the propylene / α-olefin copolymer (A2) When the total of the structural unit (a) and the structural unit (b) derived from an α-olefin having 4 or more carbon atoms is 100 mol%, the structural unit in the propylene / α-olefin copolymer (A2) ( The proportion of a) is 60 mol% or more and 95 mol% or less, and the proportion of the structural unit (b) in the propylene / α-olefin copolymer (A2) is 5 mol% or more and 40 mol% or less [4. ]
The coating material according to any one of [1] to [3], wherein the silylated polyolefin is a silylated polyolefin represented by the following formula (1).

(In the above formula (1), A ¹ , A ² and A ³ are each independently a polyolefin chain or a hydrocarbon group having 1 to 10 carbon atoms. R is a hydrocarbon group having 1 to 10 carbon atoms. Each R may be the same or different, m is an integer of 1 to 10,000, and when a plurality of A ³ are present, each A ³ may be the same or different, provided that A ¹ , A ² , A ³ represents at least one polyolefin chain.)
[5]
The content of the silylated polyolefin in the coating material is 0.005 parts by mass or more and 90 parts by mass or less with respect to 1 part by mass of the polyolefin, according to any one of the above [1] to [4]. Coating material.
[6]
The content of the polyolefin in the coating material is 0.1 to 55 parts by mass with respect to 100 parts by mass of the organic solvent, according to any one of the above [1] to [5]. Coating material.
[7]
An article comprising a coating layer formed of the coating material according to any one of [1] to [6].

  The coating material of the present invention is excellent in storage stability. Furthermore, the coating material of the present invention is easy to implement. Moreover, the coating film obtained has good coating properties and has good properties inherent to silicone (for example, coating slipperiness). Furthermore, the substrate can be coated by a simple means.

  Hereinafter, embodiments of the present invention will be described. In addition, unless otherwise indicated, the symbol "ab" which shows the numerical range in a sentence shall express from a to b or less.

Hereinafter, the coating material according to the present embodiment will be described.
The coating material according to the present embodiment includes a polyolefin having a melting point of 40 ° C. or higher and 105 ° C. or lower, a silylated polyolefin, and an organic solvent. The polyolefin and the silylated polyolefin are dissolved or dispersed in the organic solvent.
The coating material according to the present embodiment is excellent in storage stability and can impart properties expected to the silicone varnish (for example, coating slip properties) to the substrate by a simple means.

[Polyolefin]
The lower limit of the melting point (Tm) of the polyolefin according to this embodiment is 40 ° C. or higher, preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher. In addition, the upper limit of the melting point (Tm) of the polyolefin according to this embodiment is 105 ° C. or less, preferably 100 ° C. or less, and particularly preferably 97 ° C. or less. The polyolefin does not contain a silicone moiety in its constituent units.

<Measuring method of melting point>
The melting point (Tm) of polyolefin can be measured, for example, by the DSC (Differential Scanning Calorimetry) method. As the DSC device, for example, DSC-20 (manufactured by Seiko Denshi Kogyo Co., Ltd.) can be used.
First, about 10 mg of a sample is heated from −20 ° C. to 200 ° C. at 10 ° C./min, and the endothermic peak of the obtained curve is obtained as the melting point. Before the temperature rise measurement, the sample (polyolefin) is once heated to about 200 ° C., held for 5 minutes, and then cooled to room temperature (−20 ° C.) at 10 ° C./min. Polyolefin) thermal history.

Although it does not specifically limit as melting | fusing point which concerns on this embodiment in the said range, For example, the homo of ethylene or a copolymer, a propylene copolymer, etc. are mentioned.
Among these, at least one selected from an ethylene / α-olefin copolymer (A1) and a propylene / α-olefin copolymer (A2) is preferable.

In the ethylene / α-olefin copolymer (A1), the α-olefin is preferably an α-olefin having 3 or more carbon atoms, more preferably an α-olefin having 3 to 50 carbon atoms.
Examples of α-olefins include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,4- Dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1-pentene, 3,4-dimethyl-1-hexene, 4-methyl-1- Examples include heptene, 3,4-dimethyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and vinylcyclohexane.

The ethylene-derived structural unit (a) in the ethylene / α-olefin copolymer (A1) is preferably 50 to 97 mol%, more preferably 60 to 95 mol%.
Moreover, it is preferable that the structural unit (b) derived from the α-olefin in the ethylene / α-olefin copolymer (A1) is 3 to 50 mol%, and more preferably 5 to 40 mol%.
Here, the structural unit (a) + the structural unit (b) = 100 mol%.

  Moreover, it is preferable that the weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) of an ethylene * alpha-olefin copolymer (A1) exists in the range of 2,000-40,000.

  In the propylene / α-olefin copolymer (A2), the α-olefin is preferably an α-olefin having 4 or more carbon atoms, and more preferably an α-olefin having 4 to 50 carbon atoms. Examples of α-olefins include 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,4-dimethyl- 1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1-pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-heptene, Examples include 3,4-dimethyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, and the like.

The propylene-derived structural unit (a) in the propylene / α-olefin copolymer (A2) is preferably 60 to 95 mol%, more preferably 70 to 90 mol%, and 77 to 90 mol%. It is particularly preferred.
Moreover, it is preferable that the structural unit (b) derived from an α-olefin having 4 or more carbon atoms in the propylene / α-olefin copolymer (A2) is 5 to 40 mol%, and preferably 10 to 30 mol%. More preferably, it is 10-23 mol%, and it is especially preferable.
Here, the structural unit (a) + the structural unit (b) = 100 mol%.

  The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the propylene / α-olefin copolymer (A2) is preferably in the range of 3,000 to 40,000.

  A method for measuring the molecular weight of the polyolefin described above is shown below.

<Molecular weight and molecular weight distribution>
The weight average molecular weight (Mw) of the polyolefin according to this embodiment can be determined by GPC measurement. GPC measurement is performed under the following conditions. The weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene.

Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Organic solvent: o-dichlorobenzene Column: TSKgel GMH6-HT × 2, TSKgel GMH6-HTL column × 2 (both manufactured by Tosoh Corporation)
Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution Temperature: 140 ° C
Molecular weight conversion: PS conversion / general-purpose calibration method The coefficient of the Mark-Houwink viscosity equation is used for calculation of general-purpose calibration. The value described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976)) is used for the Mark-Houwink coefficient of PS (polystyrene).

The polyolefin according to this embodiment can be produced by a known method.
Further, the polyolefin according to this embodiment may be modified with an unsaturated carboxylic acid such as maleic anhydride, crotonic acid, oleic acid, or a derivative thereof.

[Silylated polyolefin]
The silylated polyolefin according to the present embodiment may have any structure as long as it has a silicone part and a polyolefin part, but preferably has a structure represented by the following formula (1).

(In the above formula (1), A ¹ , A ² and A ³ are each independently a polyolefin chain or a hydrocarbon group having 1 to 10 carbon atoms. R is a hydrocarbon group having 1 to 10 carbon atoms. Each R may be the same or different, m is an integer of 1 to 10,000, and when a plurality of A ³ are present, each A ³ may be the same or different, provided that A ¹ , A ² , A ³ represents at least one polyolefin chain.)

The polyolefin chain in A ¹ , A ² and A ³ is a polymer chain including a structural unit derived from an olefin having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms, for example.
Specific examples of the olefin having 2 to 50 carbon atoms include ethylene and an α-olefin having 3 to 50 carbon atoms (propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4 -Methyl-1-pentene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1 -Pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-heptene, 3,4-dimethyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene 1-octadecene, 1-eicocene, vinylcyclohexane, etc.).
Among these, ethylene and an α-olefin having 3 to 12 carbon atoms are preferable, ethylene and an α-olefin having 3 to 8 carbon atoms are more preferable, and ethylene is particularly preferable.
The polyolefin chain may be a homopolymer chain or a copolymer chain.

  Especially, the polymer chain comprised only from C2-C50 olefin chosen from ethylene and C3-C50 alpha olefin is preferable, Furthermore, ethylene homopolymer chain, propylene homopolymer chain, Alternatively, an ethylene / C3-C20 α-olefin copolymer chain is preferred. In the copolymer chain of ethylene / C3-C20 α-olefin, when all the structural units are 100 mol%, the structural unit derived from C3-C20 α-olefin exceeds, for example, 0 mol%. It can also be 20 mol% or less, and can also be over 0 mol% and 10 mol% or less.

  Moreover, the said polyolefin chain may also contain the structural unit derived from another olefin as needed. Other olefins include olefins containing an internal double bond such as cis-2-butene; vinylidene compounds such as isobutene; aryl vinyl compounds such as styrene; arylvinylidene compounds such as α-methylstyrene; and functionalities such as methyl methacrylate. Group-substituted vinylidene compounds; aliphatic cyclic olefins containing internal double bonds such as 5-methyl-2-norbornene, tetracyclododecene, cyclopentadiene, dicyclopentadiene; cyclic olefins containing aromatic rings such as indene; butadiene, Examples thereof include linear or cyclic polyenes such as isoprene, ethylidene norbornene and vinyl norbornene.

  The content of structural units derived from other olefins is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, assuming that all the structural units constituting the polyolefin chain are 100 mol%.

The polyolefin chain preferably has a number average molecular weight of 100 or more and 500,000 or less, more preferably 200 or more and 100,000 or less, further preferably 500 or more and 50,000 or less, and more preferably 700 or more. 10,000 or less is more preferable.
The polyolefin chain preferably has a molecular weight distribution (Mw / Mn) determined by the following GPC method in the range of 1.1 to 3.0.

<GPC measurement method>
The GPC measurement was performed using a polystyrene calibration curve using orthodichlorobenzene as a solvent at a temperature of 140 ° C., and analyzed values (weight average molecular weight (Mw), number average molecular weight (Mn) and Mw / Mn as polyethylene conversion values). ) Can be obtained.
The measurement can be performed under the following conditions. The molecular weight can be determined based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene Column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mLo-dichlorobenzene solution Temperature: 140 ° C.
Molecular weight conversion: PS conversion / general-purpose calibration method The coefficient of the Mark-Houwink viscosity equation shown below can be used for the calculation of general-purpose calibration.
Coefficient of polystyrene (PS): KPS = 1.38 × 10 ⁻⁴ , aPS = 0.70
Coefficient of polyethylene (PE): KPE = 0.06 × 10 ⁻⁴ , aPE = 0.70

In the above A ¹ , A ² , A ³ and R, examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group, an arylalkyl group, an alkenyl group, and an aryl group.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, octyl group, decyl group, and octadecyl group. A linear or branched alkyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a norbornyl group;
Examples of the arylalkyl group include a benzyl group, a phenylethyl group, and a phenylpropyl group.
Examples of the alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group.
Examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, and a naphthyl group.

  In the above formula (1), m is an integer of 1 to 10,000. m is preferably 5 or more, and more preferably 10 or more. Further, m is preferably 1,000 or less, more preferably 300 or less, and even more preferably 50 or less.

The above A ¹ , A ² , single or plural A ³ may be all polyolefin chains, or some groups may be polyolefin chains and others may be hydrocarbon groups having 1 to 10 carbon atoms. .

In the above formula (1), m is equal to or greater than 2, when at least one of A ³ that is different from the other A ^3, but plural kinds of the following units are present, not particularly limited in its aligned sequence, block Or random.

  As said formula (1), the structure represented by following (1A), (1B) or (1C) is preferable, and (1A) is more preferable among these.

(1A) In the above formula (1), A ¹ and A ² are polyolefin chains, and A ³ is a hydrocarbon group having 1 to 10 carbon atoms.
(1B) In the above formula (1), one of A ¹ and A ² is a polyolefin chain, the other is a hydrocarbon group having 1 to 10 carbon atoms, and A ³ is a hydrocarbon group having 1 to 10 carbon atoms. There is a structure.
(1C) In the above formula (1), A ¹ and A ² are hydrocarbon groups having 1 to 10 carbon atoms, and at least one of A ³ is a polyolefin chain.

  In the silylated polyolefin according to the present embodiment, the silicone part / polyolefin part (mass ratio) is not particularly limited, but is preferably, for example, 5/95 to 99/1, and more preferably 10/90 to 95/5.

  The method for producing the silylated polyolefin according to the present embodiment is not particularly limited. For example, it may be produced by the method described in paragraphs 0089 to 0145 and paragraphs 0196 to 0207 of International Publication No. 2012/098865. Can do.

[Organic solvent]
The organic solvent according to the present embodiment is not particularly limited as long as it can dissolve or disperse the polyolefin and the silylated polyolefin.
Preferred examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and decane; cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane and the like. Alicyclic hydrocarbon solvents; halogenated hydrocarbon solvents such as trichloroethylene, dichloroethylene and chlorobenzene; alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol and phenol; Ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone pentanone, hexanone, isophorone and acetophenone; Cellsolv solvents such as methyl cellosolve and ethyl cellosolve; methyl acetate, ethyl acetate and acetic acid Include; pyrrolidone solvents such as N-methyl pyrrolidone; ether solvents such as tetrahydrofuran; chill, methyl propionate, ester solvents such as butyl formate.
These may be included singly or in combination of two or more in the coating material.
Among these, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or a hydrocarbon solvent composed of an alicyclic hydrocarbon solvent, an alcohol solvent, or an ester solvent is preferable.

[Coating material]
The content of the silylated polyolefin in the coating material according to this embodiment is preferably 0.005 to 90 parts by mass, and 0.01 to 20 parts by mass with respect to 1 part by mass of the polyolefin. More preferably, it is 0.02 to 10 parts by mass, and particularly preferably 0.03 to 5 parts by mass.

  As the solute or dispersoid contained in the coating material according to the present embodiment, only the polyolefin and the silylated polyolefin may be used, but if desired, a range that does not impair the object of the present invention, for example, the total of the polyolefin and the silylated polyolefin. In the range of 10 parts by mass or less with respect to 100 parts by mass, other resins, additives and the like can be further contained.

  The content of the polyolefin in the coating material according to this embodiment is preferably 0.1 to 55 parts by mass, more preferably 1 to 40 parts by mass with respect to 100 parts by mass of the organic solvent. More preferably, it is -30 mass parts.

  The total content of the polyolefin and the silylated polyolefin in the coating material according to this embodiment is preferably 1 to 50 parts by mass and 2 to 30 parts by mass when the entire coating material is 100 parts by mass. It is more preferable, and it is especially preferable that it is 3-20 mass parts.

  A method for dissolving or dispersing the polyolefin and the silylated polyolefin according to the present embodiment in an organic solvent is not particularly limited. For example, a method in which polyolefin, silylated polyolefin, and organic solvent are mixed and stirred to dissolve and disperse polyolefin and silylated polyolefin in an organic solvent; polyolefin, silylated polyolefin, and organic solvent are mixed, A method in which the temperature is raised while stirring; further, the temperature is raised while stirring a mixture of the organic solvent, polyolefin and silylated polyolefin, and the polyolefin and silylated polyolefin are completely dissolved or partially dissolved. And a method of gradually cooling to form fine particles in an organic solvent.

  The coating material according to the present embodiment may be directly applied to an object to be coated, may be applied through an undercoat using various primers, or may be mixed with various fillers, pigments, inks, and the like. Good. Moreover, after removing a solvent once from the coating material which concerns on this embodiment, a resin component may be melt | dissolved or disperse | distributed in arbitrary solvents, and you may apply | coat to a to-be-coated article.

  When the coating material according to the present embodiment is directly applied to an object to be applied, the application method is not particularly limited, and it may be applied by spraying, or may be applied by printing or a coater. Since the coating material according to this embodiment is difficult to separate components, it can be sprayed (applied) onto the surface of an object to be coated by spray coating, for example, a spray gun. In addition, the temperature of the coating material when applying the coating material according to the present embodiment is not particularly limited, and may be applied by heating, but can also be applied at room temperature.

  The coating material which concerns on this embodiment can obtain the coating film without stickiness by drying the organic solvent contained in the said coating material after application | coating. The drying method of the coating material is not particularly limited, and may be natural drying or heat forced drying.

  When the surface of various articles is coated with the coating material according to the present embodiment, the coating surface has antifouling properties, water repellency, oil repellency, mold release properties, heat resistance, weather resistance, scratch resistance, coating slip properties, etc. Can be improved.

Although there is no special restriction | limiting in the material of the articles | goods which can apply the coating material which concerns on this embodiment, For example, a synthetic resin, an elastomer, rubber | gum, a metal, glass, ceramics, paper etc. can be mentioned.
Examples of the shape of the article include a film, a sheet, a hollow body, a fiber, a tube, and the like, but other shapes may be used.

  Examples of the use of the article coated with the coating material according to the present embodiment include electrical and electronic parts, automobile parts, building materials, containers / packaging materials, sliding parts, and release films.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples.

[Production Example 1] Production of propylene / 1-butene copolymer (A2-3) To a 2000 ml polymerization apparatus sufficiently purged with nitrogen, 900 ml of dry hexane, 65 g of 1-butene and triisobutylaluminum (1.0 mmol) were added. After charging at room temperature, the internal temperature of the polymerization apparatus was raised to 70 ° C. and pressurized to 0.7 MPa with propylene. Next, a toluene solution in which 0.002 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride and 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem) in contact with aluminum were contacted. Was added to the polymerization vessel, polymerization was carried out for 30 minutes while maintaining an internal temperature of 62 ° C. and a propylene pressure of 0.7 MPa, and 20 ml of methanol was added to terminate the polymerization. After depressurization, a polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours to obtain a propylene / 1-butene copolymer (A2-1).

  Next, 200 g of the raw material propylene / 1-butene copolymer (A2-1) produced above was put into a 1.5 L stainless steel pyrolysis apparatus equipped with a stirrer, a nitrogen inlet tube and a condenser, and the inside of the system was sufficiently replaced with nitrogen. did. Next, the temperature in the thermal decomposition apparatus was raised to 380 ° C. while flowing nitrogen, and the resin was melted, and then stirring was started. After the resin temperature in the system reached a predetermined temperature, it was heated for 4.5 hours to carry out thermal decomposition. Then, the propylene / 1-butene copolymer (A2-3) was obtained by cooling to normal temperature. Table 1 shows the physical properties of the resulting propylene / 1-butene copolymer.

[Production Example 2] Production of propylene / 1-butene copolymer (A2-4) To a 2000 ml polymerization apparatus sufficiently purged with nitrogen, 900 ml of dry hexane, 30 g of 1-butene and triisobutylaluminum (1.0 mmol) were added. After charging at room temperature, the internal temperature of the polymerization apparatus was raised to 70 ° C. and pressurized to 0.7 MPa with propylene. Next, a toluene solution in which 0.002 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride and 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem) in contact with aluminum were contacted. Was added to the polymerization vessel, polymerization was carried out for 30 minutes while maintaining an internal temperature of 62 ° C. and a propylene pressure of 0.7 MPa, and 20 ml of methanol was added to terminate the polymerization. After depressurization, a polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours to obtain a propylene / 1-butene copolymer (A2-2).

  Subsequently, it thermally decomposed similarly to manufacture example 1 except having set the temperature in a thermal decomposition apparatus to 395 degreeC, and obtained the propylene / 1-butene copolymer (A2-4). Table 1 shows the physical properties of the resulting propylene / 1-butene copolymer.

[Production Example 3] Production of propylene / ethylene copolymer (A2-5) SM668 (Titan Chemical Co.) was used as a propylene / ethylene copolymer raw material.
Subsequently, it thermally decomposed similarly to manufacture example 1, and the propylene ethylene copolymer (A2-5) was obtained. Table 1 shows the physical properties of the resulting propylene / ethylene copolymer.

[Production Example 4] Production of Ziegler-based propylene / 1-butene copolymer (A2-6) In a 2 liter autoclave sufficiently purged with nitrogen, 830 ml of hexane and 100 g of 1-butene were added, and 1 mmol of triisobutylaluminum was added. The temperature was raised to 70 ° C., and then propylene was supplied to a total pressure of 0.7 MPa, 1 mmol of triethylaluminum and 0.005 mmol of titanium catalyst supported on magnesium chloride were added in terms of Ti atoms, and propylene was continuously added. The polymerization was carried out in the same manner as in Example 1 except that the polymerization was carried out for 30 minutes while maintaining the total pressure at 0.7 MPa to obtain a Ziegler-based propylene / 1-butene copolymer (A2-6). It was. Table 1 shows the physical properties of the resulting propylene / 1-butene copolymer.

[Production Example 5] Production of ethylene / 1-butene copolymer (A2-7) 950 ml of hexane and 50 ml of 1-butene were charged into a 2-liter stainless steel autoclave sufficiently purged with nitrogen, and 1. It introduced until it became 0 kg / cm < ² > (gauge pressure). Subsequently, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.004 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate, (t-butylamido) dimethyl (tetramethyl-η5) -Cyclopentadienyl) silane titanium dichloride (manufactured by Sigma Aldrich) 0.02 mmol was injected with ethylene to initiate polymerization. Thereafter, only ethylene was continuously supplied to keep the total pressure at 30 kg / cm ² (gauge pressure), and polymerization was carried out at 150 ° C. for 20 minutes. After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene and 1-butene were purged. The obtained polymer solution was dried overnight at 100 ° C. under reduced pressure to obtain an ethylene / 1-butene copolymer (A2-7). The physical properties of the obtained ethylene / 1-butene copolymer are shown in Table 1.

[Production Example 6] Production of ethylene polymer (A2-8) In the polymerization of Production Example 5, 1000 ml of hexane and hydrogen were introduced to 1.2 kg / cm ² (gauge pressure), except that 1-butene was not introduced. Was polymerized in the same manner as in Production Example 5 to obtain an ethylene polymer (A2-8). The physical properties of the obtained ethylene polymer are shown in Table 1.

[Reference Example 1]
<Preparation of olefin-based coating material>
Into a 200 ml separable flask, 180 g of ethylcyclohexane as an organic solvent was added, and then 20 g of the propylene / 1-butene copolymer (A2-4) produced in Production Example 2 was introduced. And the mixture was allowed to cool to obtain an olefin-based coating material.

<Solubility of resin>
Preparation of the olefin-based coating material, standing still after cooling, and the solubility (room temperature) was evaluated according to the following criteria.
A: The resin was dissolved and the coating material was transparent. O: The resin was dissolved and the coating material was translucent. Δ: A part of the resin was dissolved and the rest of the polymer was dispersed. The resin was swollen, gelled or insoluble

<Standing stability>
According to the following criteria, the state of the coating material after standing at room temperature for 1 day after the preparation of the olefin-based coating material was evaluated.
○: Resin dissolved or dispersed state is maintained Δ: Part of resin is separated but easily redispersed ×: Resin is difficult to redisperse due to gelation or slurrying

<Coating property>
On the glass plate, an olefin-based coating material was applied using a film thickness variable type applicator so that the thickness of the coating film was 5 μm. And the surface state after drying at normal temperature and after drying at 140 ° C. for 1 hour was observed.
◎: The coating film was transparent and uniform ○: The coating film was turbid, but was uniform △: Part of the coating film was uneven ×: Stripes and unevenness were clearly observed on the coating film It has occurred

<Slipability of coating film>
The olefin-based coating material was applied on the glass plate by the same method as the coating property evaluation described above. And the slip property test was implemented with respect to the coating film after drying at 140 degreeC x 1 hour, and the dynamic friction and the static friction coefficient were measured according to JISK7125.

[Example 1]
<Preparation of olefinic coating material containing 5% silylated polyethylene>
Into a 200 ml separable flask, 180 g of ethylcyclohexane as an organic solvent was added, then 19 g of the propylene / 1-butene copolymer (A2-4) and 1 g of silylated polyethylene described below were added, and a stirrer on an oil bath was used. The mixture was stirred at 80 ° C. and allowed to cool to obtain an olefin-based coating material, which was evaluated in the same manner as in Reference Example 1. The results are shown in Table 2.

<Silylated polyethylene>
In the above formula (1), A ¹ and A ² are ethylene homopolymer chains (melting point (Tm) 127 ° C., Mw = 4800, Mn = 2087, Mw / Mn = 2.3), and R is a methyl group , a ³ is a methyl group, silylated polyethylene white solid is m = 12 to 13 Incidentally, silylated polyethylene was synthesized by the following methods.

[Synthesis Example 1]
According to the method described in Synthesis Example 2 of International Publication No. 2012/098865, a one-end vinyl group-containing ethylene polymer (P-1) was synthesized. The physical properties of this one-end vinyl group-containing ethylene polymer (P-1) (single unit) were as follows.
Melting point (Tm) 127 ° C
Mw = 4800, Mn = 2087, Mw / Mn = 2.3 (GPC)
Terminal unsaturation 97%

[Synthesis Example 2]
A 300 ml two-necked flask was charged with 25.1 g (11.8 mmol) of the one-end vinyl group-containing ethylene polymer (P-1) obtained in [Synthesis Example 1], and the following structure was obtained under a nitrogen atmosphere. 6.2 g (5.9 mmol; equivalent to 11.8 mmol as Si—H group) of hydrosilane A (Gelest, Inc., DMS-H11) and platinum prepared according to Synthesis Example 3 of International Publication No. 2012/098865 150 μl of the catalyst composition (C-1) diluted 200-fold with hydrosilane A (1.4 × 10 ⁻⁶ mmol in terms of Pt) was charged. The reactor was set in an oil bath that had been heated to an internal temperature of 130 ° C. in advance, and stirred. The mixture was stirred in an oil bath for 6 hours and then cooled, about 200 ml of methanol was added, and the contents were taken out into a 300 ml beaker and stirred for 2 hours. Thereafter, the solid is filtered and dried, and in the above formula (1), A ¹ and A ² are ethylene homopolymer chains, A ³ is a methyl group, R is a methyl group, and m is 33.5 g of white solid silylated polyolefin 12-13 was obtained.

Hydrosilane _{A: HSi (CH 3) 2} O - (- Si (CH 3) 2 -O-) n -Si (CH 3) 2 H (n = 12~13)

[Example 2]
<Preparation of olefin-based coating material containing 10% silylated polyethylene>
A coating material was prepared in the same manner as in Example 1 except that 18 g of the propylene / 1-butene copolymer (A2-4) and 2 g of the silylated polyethylene were used, and evaluated in the same manner as in Reference Example 1. The results are shown in Table 2.

[Example 3]
<Preparation of olefin-based coating material containing 20% silylated polyethylene>
A coating material was prepared in the same manner as in Example 1 except that 16 g of the propylene / 1-butene copolymer (A2-4) and 4 g of the silylated polyethylene were used, and evaluated in the same manner as in Reference Example 1. The results are shown in Table 2.

[Example 4]
<Preparation of 50% Silylated Polyethylene-Containing Olefin Coating Material>
A coating material was prepared in the same manner as in Example 1 except that 10 g of the propylene / 1-butene copolymer (A2-4) and 10 g of the silylated polyethylene were used, and evaluated in the same manner as in Reference Example 1. The results are shown in Table 2.

[Example 5]
<Preparation of 70% Silylated Polyethylene-Containing Olefin Coating Material>
A coating material was prepared in the same manner as in Example 1 except that 6 g of the propylene / 1-butene copolymer (A2-4) and 14 g of the silylated polyethylene were used, and evaluated in the same manner as in Reference Example 1. The results are shown in Table 2.

[Example 6]
A coating material was prepared in the same manner as in Example 1 except that 19 g of the propylene / 1-butene copolymer (A2-3) and 1 g of the silylated polyethylene were used, and the same as in Reference Example 1 except for the evaluation of the sliding property of the coating film. Evaluated. The results are shown in Table 3.

[Example 7]
A coating material was prepared in the same manner as in Example 1 except that 19 g of the above ethylene / 1-butene copolymer (A2-7) and 1 g of the above silylated polyethylene were used. Evaluated. The results are shown in Table 3.

[Comparative Example 1]
A coating material was prepared in the same manner as in Example 1 except that 19 g of the propylene / 1-butene copolymer (A2-6) and 1 g of the silylated polyethylene were used, and the same as in Reference Example 1 except for the evaluation of the sliding property of the coating film. Evaluated. The results are shown in Table 3.

[Comparative Example 2]
A coating material was prepared in the same manner as in Example 1 except that 19 g of the ethylene polymer (A2-8) and 1 g of the silylated polyethylene were used, and evaluation was performed in the same manner as in Reference Example 1 except for the evaluation of the sliding property of the coating film. The results are shown in Table 3.

[Comparative Example 3]
A coating material was prepared in the same manner as in Example 1 except that 19 g of the propylene / ethylene copolymer (A2-5) and 1 g of the silylated polyethylene were used, and evaluated in the same manner as in Reference Example 1. Evaluation was conducted in the same manner as in Reference Example 1 except for the evaluation of the sliding property of the coating film. The results are shown in Table 3.

As shown in Tables 1 to 3, the coating materials of Examples 1 to 7 containing a polyolefin having a melting point of 40 ° C. or more and 105 ° C. or less, a silylated polyolefin, and an organic solvent are soluble, stationary stability, and coating. Excellent balance of sex. In addition, as shown in Table 2, the coating materials of Examples 1 to 5 had lower kinetic friction and static friction coefficients than those of Reference Example 1 that did not contain silylated polyolefin. That is, the coating materials of Examples 1 to 5 were provided with the coating slipperiness expected for the silicone varnish.
On the other hand, the coating materials of Comparative Examples 1 to 3 containing a polyolefin having a melting point exceeding 105 ° C., a silylated polyolefin, and an organic solvent were inferior in the balance of solubility, stationary stability, and coating property.
From the above results, the coating material according to the present embodiment is excellent in storage stability and imparts properties expected of a silicone varnish (for example, coating slip properties) to the substrate by a simple means. Was found to be possible.

Claims (6)

Including a polyolefin having a melting point of 40 ° C. or higher and 105 ° C. or lower, a silylated polyolefin, and an organic solvent,
The polyolefin and the silylated polyolefin are dissolved or dispersed in the organic solvent ,
A coating material in which the silylated polyolefin is a silylated polyolefin represented by the following formula (1) .

(In the formula (1), A ¹ , A ² and A ³ are each independently a polyolefin chain or a hydrocarbon group having 1 to 10 carbon atoms. R is a hydrocarbon group having 1 to 10 carbon atoms. Each R may be the same or different, m is an integer of 1 to 10,000, and when a plurality of A ³ are present, each A ³ may be the same or different, provided that A ¹ , A ² , A ³ represents at least one polyolefin chain.)   The coating material according to claim 1, wherein the polyolefin contains at least one selected from an ethylene / α-olefin copolymer (A1) and a propylene / α-olefin copolymer (A2). The coating material according to claim 2, wherein the propylene / α-olefin copolymer (A2) satisfies the following requirements (i) and (ii).
(I) The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 3,000 to 40,000. (Ii) Propylene origin in the propylene / α-olefin copolymer (A2) When the total of the structural unit (a) and the structural unit (b) derived from an α-olefin having 4 or more carbon atoms is 100 mol%, the structural unit (A2) in the propylene / α-olefin copolymer (A2) The proportion of a) is 60 mol% or more and 95 mol% or less, and the proportion of the structural unit (b) in the propylene / α-olefin copolymer (A2) is 5 mol% or more and 40 mol% or less. The coating material according to any one of claims 1 to 3 , wherein a content of the silylated polyolefin in the coating material is 0.005 parts by mass or more and 90 parts by mass or less with respect to 1 part by mass of the polyolefin. . The coating material according to any one of claims 1 to 4 , wherein a content of the polyolefin in the coating material is 0.1 parts by mass or more and 55 parts by mass or less with respect to 100 parts by mass of the organic solvent. An article comprising a coating layer formed of the coating material according to any one of claims 1 to 5 .