WO2008018518A1

WO2008018518A1 - Fluorine-containing copolymer composition, method for producing the same, and coating composition

Info

Publication number: WO2008018518A1
Application number: PCT/JP2007/065556
Authority: WO
Inventors: Sho Masuda; Kouichi Sasaki
Original assignee: Asahi Glass Company, Limited
Priority date: 2006-08-09
Filing date: 2007-08-08
Publication date: 2008-02-14
Also published as: TW200829645A; JP2009197039A

Abstract

Disclosed is a flake-like fluorine-containing copolymer composition capable of forming a coating composition which enables to obtain a coating film having high toughness. The fluorine-containing copolymer composition has excellent blocking resistance, and can be stored at room temperature. In addition, the fluorine-containing copolymer composition exhibits high workability in redissolving, while being stable in quality. Specifically disclosed is a fluorine-containing copolymer composition which is characterized by being composed of 100 parts by mass of a resin composition (1) having a maximum particle diameter of not more than 40 mm and a 2-mm-opening sieve passing rate of not more than 10% by mass, and 0.5-3 parts by mass of a resin composition (2) having a maximum particle diameter of not more than 100 μm. This fluorine-containing copolymer composition is further characterized in that the resin composition (1) is composed of a copolymer (A) having a glass transition temperature of 30-40˚C and the resin composition (2) is composed of a copolymer (B) having a glass transition temperature of not less than 50˚C.

Description

Specification

Fluorine-containing copolymer composition, method for producing the same, and coating composition

Technical field

The present invention relates to a fluorine-containing copolymer composition and a coating composition using the same.

Background art

[0002] A coating composition using a fluorinated copolymer as a coating film component can significantly reduce the number of times of repainting in the life of the casing due to its long coating film life, and VOC generated in the product life In view of the low amount of (volatile organic compounds)! /, The demand for environmentally friendly! / Paint is increasing.

Organic solvents for paint compositions include HAPS Free (Hazardous Air Pollutants Free) solvents that are unlikely to change into air pollutants such as oxidants even when exposed to UV rays after being released into the atmosphere. Power Use is expanding mainly in the United States.

[0003] There are many types of these HAPS Free solvents, and various types are selected according to the purpose. Therefore, coating compositions using a fluorinated copolymer as a coating film component were also dissolved in various HAPS Free solvents. Things are required.

However, it is inefficient in terms of product management to supply individual fluorine-containing copolymer solvent compositions using multiple HAPS Free solvents to each fluorine-containing copolymer. In addition, it is possible to individually polymerize fluorinated copolymers using these HAPS Free solvents, but it is difficult to obtain the same molecular weight due to the chain mobility of the solvent itself. Depending on the type of solvent, the storage stability may be significantly reduced.

[0004] Therefore, after polymerization in a specific organic solvent, the polymer is dried by thin film evaporation or the like, and supplied to the customer as a flaky resin composition having a solid content concentration of 98% by mass or more. Is dissolved in any HAPS Free solvent as necessary.

According to this, since polymerization can be performed in a specific organic solvent, problems such as a change in molecular weight, a decrease in polymerization stability, and a decrease in storage stability due to the influence of the polymerization solvent can be avoided. In addition, the consumer A necessary amount of the fluorinated copolymer solvent composition can be obtained with a necessary solvent.

[0005] However, in the case of a fluorine-containing copolymer having a glass transition point of less than 40 ° C, even if it is supplied in the form of flakes, the heat receiving during transportation causes particles to adhere to each other due to the pressure due to its own weight. (Blocking) As it is, re-dissolution operation in a solvent becomes difficult. For this reason, the agglomeration step is required again, and there has been a problem that the melting work efficiency is remarkably lowered.

Using a fluorine-containing copolymer with a glass transition point higher than 40 ° C, blocking can be avoided S, and a fluorine-containing copolymer with a glass transition point of 40 ° C or lower gives a tougher coating film. easy. For this reason, there is a great demand for making a fluorinated copolymer having a glass transition point of 40 ° C or lower into flakes.

In order to solve these problems, Patent Document 1 proposes storing the powder coating composition in an environment at a temperature 20 ° C lower than the glass transition point and a relative humidity of 60% or less. Yes.

[0006] Further, as a blocking prevention technique, a technique of adding fine particle silica or wax is known. For example, Patent Documents 2 and 3 propose that a fine particle silica is added to a powder coating composition to prevent adhesion between the powder coating particles. In Patent Document 4, a fine powdery resin having an average secondary particle size of 5 m and a specific surface area of 200 to 500 m ² / g is added to the saturated polyester resin to block between sheets. Technology to prevent it has been proposed. Patent Documents 5 to 8 propose the addition of various waxes for the purpose of improving the blocking resistance of toner particles!

Patent Document 1: International Publication No. 01/25353 Pamphlet

Patent Document 2: Japanese Patent Laid-Open No. 2001-294806

Patent Document 3: Japanese Patent Laid-Open No. 2001-294807

Patent Document 4: JP-A-5-163422

Patent Document 5: JP-A-5-294629

Patent Document 6: JP-A-6-67455

Patent Document 7: JP-A-6-75422

Patent Document 8: JP-A-6-75432

Disclosure of the invention Problems to be solved by the invention

[0007] However, as in Patent Document 1, it is difficult to consistently place the raw material production to the final use place in a low temperature and low humidity state.

In addition, the particulate silica and wax used in Patent Documents 2 to 8 are too small in mass, so that a considerable amount adheres to the inner bag of polyethylene or polypropylene containers due to static electricity generated during work. End up.

Further, as a result of investigations by the present inventors, it has been found that it is difficult to uniformly mix silica and wax since the flaky resin composition has a remarkably large particle diameter with respect to the toner particles. If silica or the like cannot be mixed uniformly, it is difficult to make the composition after re-dissolution constant, and there is a problem that stable quality cannot be maintained.

Further, the present inventors tried to add fine-particle silica in which the hydroxyl group at the terminal is substituted with a methyl group in consideration of the stability and hygroscopicity of the fluorine-containing resin composition. It was confirmed that sediment was generated. This is thought to be because the terminal hydroxyl group is not completely replaced with a methyl group! /.

[0008] The present invention has been made in view of the above circumstances, can constitute a coating composition capable of obtaining a coating film with high toughness, and is excellent in blocking resistance, Provided is a fluorinated copolymer composition in the form of flakes that can be stored at normal temperature, has high workability for re-dissolution, and has stable quality.

In addition, the present invention provides a coating composition in which raw materials can be easily managed and a tough coating film can be obtained by using this fluorine-containing copolymer composition. Means for solving the problem

[0009] As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a copolymer having a high glass transition point having a monomer composition similar to that of a copolymer having a low glass transition point has been obtained. The idea was to add the coalescence as a blocking inhibitor. That is, the present invention has the following gist.

[0010] [1] 100 parts by mass of a resin composition (1) having a maximum particle size of 40 mm or less and a 2 mm aperture sieve passing rate of 10% by mass or less, and a resin composition having a maximum particle size of 100 or 1 m or less (2 0.5-3 parts by mass of The resin composition (1) strength One or more monomers (al) selected from black trifluoroethylene and tetrafluoroethylene, butyl ethers, butyl esters, propenyl ethers and propyl ethers Comprising a copolymer (A) having a glass transition point of 30 to 40 ° C., which is obtained by polymerizing at least one monomer (a2) selected from the group consisting of phenyl esters, 2) polymerizes the same monomer (bl) as the monomer (al) and one or more monomers (b2) selected from the group consisting of butyl ethers and butyl esters. Made of a copolymer (B) having a glass transition point of 50 ° C or higher,

A fluorine-containing copolymer composition characterized by the above.

[2] The solid content concentration of the resin composition (1) is 98.5% by mass or more, and the solid content concentration of the resin composition (2) is 98.5% by mass or more. Fluorine-containing copolymer composition.

[3] The amount of monomer (a2) used in the production of copolymer (A) is 40 to 60 mol% of the total amount of monomers. Fluorine copolymer composition.

[4] The amount of the monomer (b2) used in the production of the copolymer (B) is 40 to 60 mol% of the whole monomer. The fluorine-containing copolymer composition according to any one of the above.

[5] In the resin composition (2), the content ratio of particles having a particle size of 5 am or more is 80% by mass or more of the whole particles. Fluorine copolymer composition.

[6] The resin composition (2) above having a mass average particle diameter of 15 to 30 m and 1 m. ] To [5] !, or the fluorine-containing copolymer composition according to any one of the above.

[7] From one or more monomers (al) selected from black-trifluoroethylene and tetrafluoroethylene, and bull ethers, bull esters, propenyl ethers and propenyl esters A copolymer (A) having a glass transition point of 30 to 40 ° C. obtained by polymerizing at least one monomer ( _a 2) selected from the group consisting of A pulverizing step (1) for forming a flaky resin composition (1) having a 2 mm aperture sieve passage rate of 10% by mass or less,

A glass transition obtained by polymerizing the same monomer (bl) as the monomer (al) and one or more monomers (b2) selected from the group consisting of butyl ethers and butyl esters. A powdery resin composition with a maximum particle size of 100 m or less by pulverizing the copolymer (B) having a point of 50 ° C or higher Crushing process (2),

100 parts by mass of the flaky resin composition (1) and the powdery resin composition (2) 0.5 to

Mixing 3 parts by mass,

The manufacturing method of the fluorine-containing copolymer composition which has this.

[8] The method for producing a fluorinated copolymer composition according to the above [7], comprising a step of sieving / separating the obtained powdered resin composition (2) after the pulverization step (2).

[9] A coating composition characterized by containing the fluorine-containing copolymer composition according to any one of [1] to [6] above.

The invention's effect

[0011] The fluorine-containing copolymer composition of the present invention can constitute a paint composition capable of obtaining a coating film with high toughness, has excellent blocking resistance, can be stored at room temperature, and is specially stored. No conditions are required. In addition, since re-dissolution is easy, it is possible to appropriately re-dissolve in any solvent as needed without preparing a solvent composition of a large number of fluorine-containing copolymers using various solvents. Power S can be. Moreover, the quality is stable.

In addition, since the coating composition of the present invention can obtain a coating film with high toughness by using the fluorine-containing copolymer composition of the present invention, it is easy to manage raw materials. Manufacturing cost is low. Moreover, the quality is stable.

Brief Description of Drawings

FIG. 1 is a diagram for explaining a test method of a blocking test.

Explanation of symbols

[0013] 1 ... cylinder, 2 ... stopper, 3 ... piston, S ... sample

BEST MODE FOR CARRYING OUT THE INVENTION

[Fluorine-containing copolymer composition]

The fluorine-containing copolymer composition of the present invention is a mixture of the resin composition (1) and the resin composition (2) (hereinafter referred to as a mixture of the resin composition (1) and the resin composition (2)). The resin composition (1) may be 100 parts by mass and the resin composition (2) is 0.5 to 3 parts by mass. In both resin composition (1) and resin composition (2), it is preferable that no solvent derived from the polymerization solvent remains. Specifically, the volatile matter derived from the solvent or the like is less than 1.5% by mass, preferably S, and more preferably less than 1% by mass. That is, when the solid content concentration in the resin composition (1) and the resin composition (2) is 98.5% by mass or more, it can be distributed and stored in the form of a flaky resin composition. Preferable because it can sometimes be redissolved in any solvent.

[0015] The solid content concentrations of the resin composition (1) and the resin composition (2) are each preferably 99% by mass or more. Low solid content means that the amount of solvent contained is large, and in that case, the blocking resistance is lowered. In addition, when the resin composition (3) having a low solid content concentration is redissolved, a solvent different from the solvent used for the redissolution (usually a polymerization solvent) cannot be ignored! This will affect the properties of the solvent composition in which the product (3) is redissolved and the properties of the coating composition obtained using the same.

[0016] <Resin composition (1)>

The solid content of the resin composition (1) is the copolymer (A). The resin composition (1) has a maximum particle size force of Omm or less and a 2 mm sieve sieve passage rate of 10% by mass or less.

[0017] <Copolymer (A)>

Copolymer (A) is a copolymer obtained by polymerizing monomer (al) and monomer (a2). The glass transition point of copolymer (A) is 30-40 ° C.

[0018] The monomer (al) is selected from black trifluoroethylene (CTFE) and tetrafluoroethylene (TFE) force. CTFE or TFE can be used alone or in combination!

In the present invention, hexafluoropropylene (HFP) that can be used for general fluorine-containing copolymers is not used as the monomer (al). This is because the glass transition point of the copolymer (B) described later is 50 ° C. or higher, and the monomer (bl) used for this is the same as the monomer (al).

When HFP is used as the monomer (al), it is possible to obtain a copolymer with a glass transition point of 30-40 ° C. Obtain a copolymer with a glass transition point of 50 ° C or higher. It is difficult

Yes

By making the monomer (al) one or more selected from CTFE and TFE, a copolymer The glass transition point of (A) is 30-40 ° C, and the copolymer (B) is the same type of monomer (bl) as the monomer (al). Can do.

[0019] The monomer (a2) is one or more monomers selected from the group consisting of butyl ethers, butyl esters, propenyl ethers, and propenyl esters. Monomer ( _a

2) Any one of these monomers may be used, or two or more may be used.

[0020] Bull ethers are compounds represented by the following formula (1).

CH = CHOR ¹ ---(l)

2

[However, R ¹ in the formula (1) is a linear or branched alkyl group or a cyclic hydrocarbon group, and any of them may have a hydroxyl group. ]

R ¹ is more preferably an alkyl group having 4 to 5 carbon atoms, preferably an alkyl group having 2 to 8 carbon atoms.

Specific examples of burethers include

Hydroxy quineno levino renenoate, such as hydroxy chineno vinino ree noate, hydroxy neo pentino levino ree noate;

Hydroxycycloanolequinolevininoreethenoles such as cyclohexenoremethinorevininoreethenoremonomethinoleanorecoinole ([4- (vinyloxymeth yl) cyclohexyl]) methan— 1—ol) tert-butinorevininore Ethenore, isobutino revino eno enolet, neopentino levino ole eno enore, 2-ethino lepropino revino eno enore, ethino levino ree noeno, n-butino revino eno eno nore, cyclohexeno leveno eno Examples thereof include alkyl butyl ethers such as 2-ethinorehexinorevininoreethenole.

[0021] Bull esters are compounds represented by the following formula (2).

R ² COOCH = CH

2

[However, R ² in the formula (2) is a linear or branched alkyl group or a cyclic hydrocarbon group, and any of them may have a hydroxyl group. ]

R ² is more preferably an alkyl group having 3 to 4 carbon atoms, preferably an alkyl group having 2 to 11 carbon atoms.

Specific examples of bulule esters include bivalerate bur, isobutyric bur, isovaleric And acid butyl, hydroangelic acid butyl, versatic acid butyl, and p-tert-butyl benzoate.

[0022] The propenyl ethers are compounds represented by the following formula (3) or the following formula (4). Among these, the compound power represented by the following formula (3) is preferable because of excellent copolymerizability with the monomer (al).

Yes

CH = C (CH) OR ³ ---(3)

twenty three

CH CH = CHOR ⁴ ---(4)

Three

[However, R ³ in the formula (3) and R ⁴ in the formula (4) are each independently a linear or branched alkyl group or a cyclic hydrocarbon group, both of which are hydroxyl groups. You may have. ]

R ⁴ is more preferably an alkyl group having 1 carbon atom, preferably an alkyl group having 2 to 6 carbon atoms.

Specific examples of propenyl ethers include 2-methoxypropene.

[0023] The propenyl esters are compounds represented by the following formula (5) or the following formula (6).

CH = C (CH) OOCR ⁵ ---(5)

twenty three

CH CH = CHOOCR ⁶ ---(6)

Three

[However, R ⁵ in the formula (5) and R ⁶ in the formula (6) are each independently a linear or branched alkyl group or a cyclic hydrocarbon group, both of which are hydroxyl groups. You may have. ]

R ⁵ and R ⁶ are each preferably an alkyl group having 4 to 4 carbon atoms, more preferably an alkyl group having 3 to 4 carbon atoms.

[0024] The glass transition point of the copolymer (A) is 30 to 40 ° C, preferably 35 to 40 ° C. In the present invention, since the copolymer (A) is the main component of the resin composition (3), the glass transition point of the copolymer (A) greatly contributes to the overall properties of the resin composition (3)! /.

When the glass transition point of the copolymer (A) is less than 30 ° C, the flake shape may not be maintained at room temperature even if the resin composition (3) is dried to increase the solid content concentration. Further, when the glass transition point of the copolymer (A) is 40 ° C. or less, the toughness of the coating film obtained from the coating composition using the resin composition (3) is increased.

[0025] The glass transition point of the copolymer (A) can be controlled by the type and molecular weight of the monomer (a2). In general, when a monomer having a side chain that suppresses the degree of freedom of the main chain is introduced, the glass transition point increases, so in the above formulas (1) to (6)! The glass transition point can also be controlled by appropriately selecting ^ ˜.

[0026] Since the glass transition point increases as the molecular weight increases, the glass transition point can also be controlled by adjusting the molecular weight of the copolymer (A). However, in order for the resin composition (3) to have a flake shape, the number average molecular weight of the copolymer (A) is preferably 5500 or more, more preferably 6500 to 22000, from the force S. Therefore, it is preferable to adjust the molecular weight within the preferable range.

The molecular weight can be controlled by the amount of initiator and chain transfer agent used during polymerization, the ratio of monomer to solvent, and the like.

[0027] The copolymer (ii) is obtained by polymerizing the monomer (al) and the monomer (a2) by a known method. For example, a polymerization initiator such as a polymerization initiator or ionizing radiation is allowed to act on a mixture containing monomer (al) and monomer (a2) in a predetermined ratio in the presence or absence of a polymerization solvent. Can be produced by carrying out a copolymerization reaction.

The amount of the copolymer monomers in the preparation of (A) (a2) is a copolymer preferably has 40 to 60 mole ^_0/0 of the total monomers constituting the (A) tools 45 The preferred than 55 mole ^_0/0 force S. When the amount of the monomer (a2) used is within the above range, the solubility in an organic solvent is excellent, and the weather resistance of the coating film is excellent.

As the polymerization solvent, xylene, ethanol, tert-butanol, acetone, methyl ethyl ketone, ethoxyethyl propionate, CFHC1, or the like can be used.

3 5 2

As the initiator, peroxides such as peroxybutyl bivalate, azo initiators such as azobisisobutyl nitrile, and the like can be used.

Drying is performed after the copolymerization reaction. Drying is performed with a force of s by thin film evaporation, vacuum evaporation, spray drying, etc.

[0028] <Granularity>

The resin composition (1) has a maximum particle size of 40 mm or less and a 2 mm sieve sieve passage rate of 10 mass% or less.

If the maximum particle size exceeds 40 mm, the time required for dissolution during re-dissolution will be significantly longer. The maximum particle size is more preferably 35 mm or less. On the other hand, when the passing rate of 2 mm openings exceeds 10% by mass, blocking tends to occur due to the large number of particles having a large specific surface area. Therefore, unless the resin composition (2) is added in an amount of more than 3 parts by mass with respect to 100 parts by mass of the resin composition (1), sufficient blocking resistance cannot be obtained. The passage rate of 2 mm openings is more preferably 8% by mass or less.

The mass average particle diameter of the resin composition (1) is preferably 10 to 25 mm, more preferably 10 to 20 mm! /.

Each numerical value relating to the particle size of the resin composition (1) is obtained by mass measurement by a sieve mesh method. Here, the sieve mesh method is a method in which a sample is put into a stainless steel sieve having a target mesh (mesh), vibrated for 2 minutes, and then the mass passing through the mesh is measured.

Yes

[0029] <Crushing distance 1>

The particle size of the resin composition (1) is controlled by pulverization conditions. That is, the resin composition (1) is obtained by drying the copolymer (A) obtained by polymerization to a solid content concentration of 98.5% by mass or more, then forming a plate with a cooling roll or the like in a molten state, It can be obtained by crushing using a crusher such as a pink lasher. The adjustment of the particle size is controlled by the number of revolutions of the agglomerator and the opening of the comb teeth.

For example, if the plate-shaped copolymer (A) is passed through a pink lasher having a comb tooth of 15 mm opening and rotating at 100 revolutions per second for 1 second, the maximum particle size becomes 25 to 40 mm, 2 mm Opening sieve passing rate is in the range of 1 to 10% by mass.

[0030] <Resin composition (2)>

The solid content of the resin composition (2) is the copolymer (B). The maximum particle size of the resin composition (2) is 100 m or less.

[0031] <Copolymer (B)>

The copolymer (B) is a copolymer obtained by polymerizing the monomer (bl) and the monomer (b2). The glass transition point of copolymer (B) is 50 ° C or higher.

[0032] The monomer (bl) is the same type of monomer as the monomer (al). That is, when monomer (al) is CT FE alone, monomer (bl) is also CTFE alone, and monomer (al) is TFE alone. In some cases, monomer (bl) is also TFE alone, and when monomer (al) is a combination of CTFE and TFE, monomer (b 1) is a combination of CTFE and TFE.

When the monomer (bl) is the same type of monomer as the monomer (al), compatibility between the resin composition (1) and the resin composition (2) can be obtained.

When monomer (al) is a combination of CTFE and TFE, from the viewpoint of ensuring compatibility, the ratio of CTFE to TFE of monomer (bl) is the ratio of CTFE to TFE of monomer (al). As close as possible, that power S is preferred, and it is particularly preferred to be the same! / ,.

As described above, by selecting the monomer (bl) from CTFE and TFE, the glass transition point of the copolymer (B) can be set to 50 ° C or higher.

[0033] The monomer (b2) is selected from the group consisting of butyl ethers and butyl esters.

One or more monomers. Monomer (b2) may be any one of these monomers, and one or more may be used.

The bull ethers and the bule esters can be selected from the same compounds as those shown in the description of the monomer ( _a 2).

Since the glass transition point of the copolymer (B) is 50 ° C or higher, it is difficult to make the monomer (b2) the same type and the same ratio as the monomer (a2). However, from the viewpoint of ensuring the compatibility of the resin composition (1) and the resin composition (2), the monomer (b2) is preferably selected from the same type of monomer as the monomer (a2). Better!/,.

The monomer (b2) preferably has a methyl group, a cyclohexyl group or a tert-butyl group because a high glass transition point is obtained. Further, those having a hydroxyethyl group or a hydroxy n-butyl group as the crosslinking reaction site are preferred.

[0034] The glass transition point of the copolymer (B) is 50 ° C or higher, preferably 5;! To 70 ° C.

By being 50 ° C or higher, it can function as a blocking-resistant agent that does not melt at room temperature. Further, if it is 70 degrees or less, it is expected that the polymerization sites of the monomers (b2) are not so many and the possibility of existing as crystal sites is low, and the transparency of the entire resin composition is increased. I like it.

[0035] The glass transition point of the copolymer (B) is the same as the glass transition point of the copolymer (A)! /, As described above, by the type and molecular weight of the monomer (b2). Be controlled. By using butyl ethers and / or butyl esters as the monomer (b2), the glass transition point of the copolymer (B) can be set to 50 ° C. or higher.

In addition, the above formulas (1) and (2)

Even cowpea the appropriate selection of the R ² can control the glass transition point.

[0036] Since the glass transition point increases as the molecular weight increases, the glass transition point can also be controlled by adjusting the molecular weight of the copolymer (B). However, in order for the resin composition (3) to have a flake shape, the number average molecular weight of the copolymer (B) is preferably 5500 or more, more preferably 6500 to 22000, from the force S. Therefore, it is preferable to adjust the molecular weight within this range.

The molecular weight is controlled by the amount of initiator and chain transfer agent used during polymerization, the ratio of monomer to solvent, etc.

[0037] The copolymer (Β) is obtained by polymerizing the monomer (bl) and the monomer (b2) by a known method.

For example, a polymerization initiator or a polymerization initiator such as ionizing radiation acts on a mixture containing monomer (bl) and monomer (b2) in a predetermined ratio in the presence or absence of a polymerization solvent. And can be produced by carrying out a copolymerization reaction.

The amount of the monomer (b2) in the production of the copolymer (B), copolymer (B) preferably is from 40 to 60 mole ^_0/0 of the total monomers constituting the instrument 45 The preferred than 55 mole ^_0/0 force S. When the amount of the monomer (b2) used is within the above range, the solubility in an organic solvent is excellent, and the weather resistance of the coating film is excellent.

As the polymerization solvent and initiator, the same solvents as those used for the polymerization of the copolymer (A) can be used. Drying after the copolymerization reaction can be performed in the same manner as for the copolymer (A).

[0038] <Granularity>

The resin composition (2) has a maximum particle size of 100 m or less.

When the maximum particle size exceeds 100 πι, the resin composition (1) is coated. In addition, since its own weight increases, even if the resin composition (2) is coated, it is easily removed due to vibration during transportation. For this reason, the resin composition (2) has a low function as an anti-blocking agent. I will give you. More preferably, the maximum particle size is 90 m or less!

The content ratio of particles having a particle size of 5 am or more in the resin composition (2) is preferably 80% by mass or more of the whole particles, more preferably 90% by mass or more. As a result, the amount of the resin composition (2) adhering to the packaging material due to static electricity generated during mixing can be reduced, and the amount of the resin composition (2) covering the resin composition (1) is sufficient. Can be secured.

Each numerical value relating to the particle size of the resin composition (2) is determined by a laser diffraction particle size distribution analyzer. Examples of such measuring machines include Microtrac (trade name of Nikkiso Co., Ltd.), Master Mizer 1 (trade name of Malvern Instruments Ltd.), and HELOS-RODOS (trade name of Sympatech).

[0039] <Crushing step 2>

The particle size of the resin composition (2) is controlled by pulverization conditions and sieve openings. That is, the resin composition (2) is obtained by drying the copolymer (B) obtained by polymerization to a solid content concentration of 98.5% by mass or more and then forming a plate with a cooling roll or the like in the molten state. It can be obtained by pulverizing with a pulverizer such as a pink rusher and further pulverizing with a pulverizer, and then sieving the particles.

The maximum particle size is controlled by the sieve opening. The ratio of the particles of 5 am or less and the mass average particle diameter are controlled by the number of revolutions of the pulverizer, the pulverization time, and the sieve opening. For example, using a small pulverizer with a crushing blade rotation method, pulverizing at 12000 rpm for 10 seconds and then sieving once with a 200 mesh sieve (86 m mesh), the mass of the resin composition (2) after passing through The average particle size is in the range of 15-30111.

[0040] «Production of resin composition (3)»

The resin composition (3) is contained in the container in an amount of 0.5 to 3 parts by mass, preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the resin composition (1) and the resin composition (1). It is obtained by charging the resin composition (2) and shaking the container. Cardboards, fiber drums, paper bags, etc. with polyethylene or polypropylene as inner bags are used as containers.

In the present invention, the mass parts of the resin composition (1) and the resin composition (2) are put into a container. The amount of mass part is shown. This is because a part of the charged resin composition (2) does not adhere to the resin composition (1) but adheres to the inner bag due to the charging phenomenon caused by friction with the inner bag of the container. This is because it is difficult to determine the amount substantially attached to 1).

[0041] By using 0.5 parts by mass or more of the resin composition (2) with respect to 100 parts by mass of the resin composition (1), the resin composition (2) is spread over the entire resin composition (1). In addition, the effect of preventing blocking of the resin composition (2) can be exhibited.

On the other hand, for 100 parts by mass of resin composition (1), more than 3 parts by mass of resin composition (2)

V is preferable because the influence of the resin composition (2) on the overall properties of the resin composition (3) becomes remarkable! Specifically some cases force ^s turbidity occurs upon re-dissolved resin composition (3).

[0042] [Coating composition]

The coating composition of the present invention contains the fluorine-containing copolymer composition (resin composition (3)) of the present invention. In addition to the resin composition (3), a solvent and various additives can be contained.

Since the resin composition (3) has a solid content concentration of 98.5% by mass or more, any solvent can be used. Examples thereof include tert-butyl acetate, chlorobenzene trifluoride, ethoxyethyl propionate and the like. Two or more of these may be used in combination. Additives include titanium dioxide, iron oxide, carbon black, pearl pigment, phthalocyanine copper complex, quinacridone, benzimidazolone, perylene, dioxazine, metal oxide complexes, metallic pigments, pigments such as silica; polyisocyanate, Curing agents such as melamine; additives such as leveling agents, anti-craters, rheology modifiers, gloss modifiers, slipping agents, water repellents, water repellents, hydrophilizing agents, pigment dispersants, curing catalysts, etc. Can be used in appropriate combinations.

The coating composition of the present invention is produced by mixing the resin composition (3) with additives as necessary, and then mixing and dispersing with a solvent. In addition, the resin composition (3) obtained by re-dissolving only the solvent can be used as a paint vehicle.

A coating film is formed by applying the coating composition of the present invention to an article to be coated by a method such as spraying or brushing and then drying. Example

[0043] The present invention is described in detail below, but the present invention is not construed as being limited thereto.

In an autoclave with a stainless steel stirrer with an internal volume of 2500 mL, l lg of potassium carbonate, 206 g of ethyl butyl ether (EVE), 129 g of hydroxybutyl butyl ether (HBVE), and 208 g of cyclohexyl butyl ether (CHVE) And a monomer mixture, 587 g of xylene, 168 g of ethanol, and 66 Og of black trifluoroethylene (CTFE).

Next, the temperature was gradually raised, and after reaching 65 ° C, 15 g of a 10% by mass xylene solution of tert-butyl peroxybivalate (PBP V) was added over 11 hours, and then maintained for 13 hours. Thereafter, the mixture was cooled and filtered to remove the residue to obtain a copolymer (A1). The resulting xylene solution of copolymer (A1) was evaporated in a thin film and dried to a solids concentration of 99% by mass.

[0044] The dried copolymer (A1) thus obtained had a number average molecular weight (Mn) of 13,000 according to gel permeation chromatograph (GPC, HLC-8220-GPC manufactured by Tosoh Corporation). The glass transition point (Tg) force by a differential calorimeter (DSC, manufactured by Seiko Instruments Inc., DSC6200) was ¾4 ° C.

Table 1 shows the raw material composition used for the production of the copolymer (A1), the number average molecular weight (Mn) and the glass transition point (Tg) of the copolymer (A1).

[0045] <Production of copolymer (B1)>

Into an autoclave with a stainless steel stirrer with an internal volume of 2500 mL, a monomer mixture of 12 g of potassium carbonate, 145 g of hydroxybutyl butyl ether (HBVE) and 558 g of cyclohexyl butyl ether (CHVE), 503 g of xylene, ethanol Then, gradually warmed up to 65 ° C, and then added 14 g of a 10% by weight xylene solution of tert-butyl peroxybivalate (PBP V) over 8 hours, then 16 hours Retained. Thereafter, the mixture was cooled and filtered to remove the residue to obtain a copolymer (B1). The resulting xylene solution of copolymer (B1) was evaporated in a thin film and dried to a solid content concentration of 98.5% by mass.

[0046] The dried copolymer (B1) thus obtained had a number average molecular weight (Mn) of 13,200 by gel permeation chromatography (GPC) and was measured by a differential calorimeter (DSC). The glass transition point (Tg) force was ¾2 ° C.

Table 1 shows the raw material composition used for the production of the copolymer (B1), the number average molecular weight (Mn) and the glass transition point (Tg) of the copolymer (B1).

[0047] [Table 1]

<< Flake Resin Composition >>

The dried copolymer (A1) in the form of a plate is passed through a pink lasher having a comb tooth with a 20 mm mesh and rotating at 100 rpm for 1 second to give a flaky resin composition (A1 — I got 1). The maximum particle size of the obtained flaky resin composition (A1-1) is 35 mm. The passing rate through a 2 mm mesh sieve was 8% by mass.

[0049] <Manufacture of flaky resin composition (B1-1)>

The dried copolymer (B1) in the form of a plate is passed through a pink lasher having a comb tooth with a 20 mm aperture and rotating at 100 rpm for 1 second to give a flaky resin composition (lb ) The obtained flaky resin composition (Bl-1) had a maximum particle size of 35 mm and a passing rate of 2 mm mesh sieve was 7% by mass.

[0050] << Powdered resin composition >>

The flaky resin composition (A1-1) was crushed for 10 seconds at 12000 rpm using a crushing blade rotation type small pulverizer, then sieved with a 200 mesh sieve (86 m mesh), and the sieved excess was pulverized. A powdery resin composition (A1-2) was obtained.

The maximum particle size of the obtained powdery resin composition (A1-2) measured with a laser diffraction particle size distribution analyzer (HELO S-RODOS, manufactured by Sympatech) is 95 m, and the mass average particle size is 23 11 m. I did it.

[0051] <Production of powdered resin composition (B1-2)>

The flaky resin composition (B1-1) was pulverized for 10 seconds at 12000 rpm using a small pulverized blade rotation type pulverizer, then sieved with a 200 mesh sieve (86 m mesh), and the sieved excess was pulverized. A powdery resin composition (B1-2) was obtained.

The powdered resin composition (B1-2) obtained had a maximum particle size of 95 Hm and a mass average particle size of 25 m as measured by a laser diffraction particle size distribution analyzer.

[0052] << Sample >>

In a 0.5 L container made of polyethylene, add 50 g (100 parts by mass) of the flaky resin composition (Al-1) and 1.5 g (3 parts by mass) of the powdered resin composition (B1-2). The sample 1 was obtained by adding and shaking.

[0053] <Sample 2>

In a 0.5 L container made of polyethylene, 50 g (100 parts by mass) of the flaky resin composition (Al-1) and 0.25 g (0.5 part by mass) of the powdered resin composition (Bl-2) ) And sample 2 was obtained.

[0054] <Sample 3>

Sample 3 was made up of 50 g (100 parts by mass) of the flaky resin composition (A1-1).

[0055] <Sample 4>

In a 0.5 L container made of polyethylene, add 50 g (100 parts by mass) of the flaky resin composition (Al-1) and 2.5 g (5 parts by mass) of the powdered resin composition (B1-2). The sample 4 was obtained by adding and shaking.

[0056] <Sample 5>

In a 0.5 L container made of polyethylene, add 50 g (100 parts by mass) of the flaky resin composition (Al-1) and 1.5 g (3 parts by mass) of the powdered resin composition (A1-2). The sample 5 was obtained by adding and shaking.

[0057] <Sample 6>

In a 0.5 L container made of polyethylene, 0.5 g of 50 g (100 parts by mass) of the flaky resin composition (Al-1) and hydrophobic fine powder silica (product name: AEROSIL R 972, manufactured by Nippon Aerosil Co., Ltd.) Sample 6 was obtained by adding 15 g (0.3 parts by mass) and shaking.

[0058] << Evaluation >>

The following tests were performed on each of the obtained samples.

As shown in Fig. 1, a cork stopper 2 is placed on one side of an acrylic cylinder 1 with an inner diameter R force of 4 mm, and 50 g of each sample S is placed in it. Purchased 3. Further, a load was applied so that the total of the piston 3 and the piston 3 was 890 g (59 g / cm ² ), and it was left in a constant temperature bath at 35 ° C. for 4 days.

After that, the cake of each sample formed was taken out, dropped from a height of 30 cm onto a concrete lined with vinyl chloride, and examined whether or not it collapsed. The thing was rated as X.

[0059] <Re-dissolution test>

Each sample after the blocking test (force that did not collapse due to the blocking test, was applied to the other sample! /, And was further destroyed by hitting with a plastic hammer) It was dissolved in Len at a concentration of 50% by mass, and the state of the solution was observed.

[0060] Table 2 shows the raw material composition and evaluation results of each sample.

[0061] [Table 2]

[0062] In the sample 3 consisting only of the flaky resin composition (A1-1) having a glass transition point (Tg) of 34 ° C, blocking S occurred, and the glass transition point (Tg) was 52 ° C. Samples 1 and 2 to which 0.5 to 3% by mass of the powdery resin composition (B1-2) was added showed an anti-blocking effect, and the state after re-dissolution was also abnormal.

On the other hand, in sample 4 where the amount of the powdered resin composition (B1-2) added was 5% by mass, the anti-blocking effect was observed. After re-dissolution, the solution became cloudy! . Further, blocking occurred in Sample 5 in which 3% by mass of the powdery resin composition (A1-2) having a glass transition point (Tg) of 34 ° C. was added to the flaky resin composition (A1-1).

Further, in Sample 6 in which fine powder silica was added to the flaky resin composition (Al-1), a precipitate was confirmed after re-dissolution of the force, which showed an anti-blocking effect.

Industrial applicability

[0063] The fluorine-containing copolymer composition of the present invention is excellent in blocking resistance, can be stored at room temperature, does not require special storage conditions, has stable quality, and is necessary for any solvent. It can be redissolved accordingly. Furthermore, a coating composition using this is suitable for obtaining a coating film having high toughness, and is extremely useful in industry. The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2006-216934, filed on August 9, 2006, are incorporated herein by reference. It is included as an indication.

Claims

The scope of the claims

[1] Resin composition (1) having a maximum particle size of 40 mm or less and a 2 mm aperture sieve passage rate of 10 mass% or less and a resin composition (2) having a maximum particle size of 100 m or less (0.5) Consisting of mass parts,

The resin composition (1) strength One or more monomers (al) selected from black trifluoroethylene and tetrafluoroethylene, butyl ethers, butyl esters, propenyl ethers and propyl ethers The resin composition (A) comprising a copolymer (A) having a glass transition point of 30 to 40 ° C., which is obtained by polymerizing one or more monomers (a2) selected from the group consisting of phenyl esters. 2) polymerizes the same monomer (bl) as the monomer (al) and one or more monomers (b2) selected from the group consisting of butyl ethers and butyl esters. Made of a copolymer (B) having a glass transition point of 50 ° C or higher,

A fluorine-containing copolymer composition characterized by the above.

[2] The fluorine-containing composition according to claim 1, wherein the solid content concentration of the resin composition (1) is 98.5% by mass or more, and the solid content concentration of the resin composition (2) is 98.5% by mass or more. Copolymer composition.

[3] The amount of the monomer (a2) used in the production of the copolymer (A) is 40 to 40% of the total monomers.

The fluorine-containing copolymer composition according to claim 1 or 2, which is 60 mol%.

[4] When the copolymer (B) is produced, the amount of the monomer (b2) used is 40 to 40% of the total monomers.

The fluorine-containing copolymer composition according to any one of claims 1 to 3, which is 60 mol%.

[5] In the resin composition (2), the content ratio of particles having a particle diameter of 5 am or more is

The fluorine-containing copolymer composition according to any one of claims 1 to 4, which is 80% by mass or more.

6. The fluorine-containing copolymer composition according to any one of claims 1 to 5, wherein the resin composition (2) has a mass average particle diameter of 15 to 30 m.

[7] Group consisting of one or more monomers (al) selected from black-trifluoroethylene and tetrafluoroethylene, and bull ethers, bull esters, propenyl ethers and propenyl esters A copolymer (A) having a glass transition point of 30 to 40 ° C, which is obtained by polymerizing at least one monomer ( _a2 ) selected from the above, is pulverized, and the maximum particle size is 40 mm or less.

A pulverization process (1) to make a flaky resin composition (1) having a 2 mm aperture sieve passage rate of 10% by mass or less, A glass transition obtained by polymerizing the same monomer (bl) as the monomer (al) and one or more monomers (b2) selected from the group consisting of butyl ethers and butyl esters. A pulverization step (2) for pulverizing a copolymer (B) having a point of S50 ° C or higher to obtain a powdery resin composition (2) having a maximum particle size of 100 m or less,

Mixing 3 parts by mass,

8. The method for producing a fluorinated copolymer composition according to claim 7, further comprising a step of sieving and separating the obtained powdered resin composition (2) after the pulverizing step (2).

[9] A coating composition comprising the fluorine-containing copolymer composition according to any one of claims 1 to 6.