CN106957392B - Curable resin composition for blind road sticker, and method for producing blind road sticker - Google Patents
Curable resin composition for blind road sticker, and method for producing blind road sticker Download PDFInfo
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- CN106957392B CN106957392B CN201611083080.7A CN201611083080A CN106957392B CN 106957392 B CN106957392 B CN 106957392B CN 201611083080 A CN201611083080 A CN 201611083080A CN 106957392 B CN106957392 B CN 106957392B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C15/00—Pavings specially adapted for footpaths, sidewalks or cycle tracks
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Abstract
Provided is a curable resin composition for a blind road application, which has a viscosity and a gelation time suitable for molding, has low hardness, and is excellent in strength and elongation. A curable resin composition for a blind road sticker, which is produced into a sheet-like cured product for evaluation by the following method, wherein the cured product is evaluated to have a hardness of D15-D65, a tensile strength of 5-50 MPa, and an elongation at break of 120-1000%; method for producing evaluation-use sheet-like cured product: after vacuum defoaming the curable resin composition, the resin composition was poured into a glass interlayer made of 2 glass plates covered with a PET film and a vinyl chloride gasket, cured at 23 ℃ for 12 hours, and after curing, the glass and PET film on both sides were removed to obtain a sheet-like cured product having a length of 250mm, a width of 250mm, and a thickness of 3 mm.
Description
Technical Field
The present invention relates to a curable resin composition for a blind road patch, and a method for producing a blind road patch.
Background
For the purpose of helping visually impaired people to move safely and comfortably, guidance instructions such as blind tiles or blind patches are laid on the ground and floor of platforms and sidewalks, public facilities, commercial facilities, and the like at stations. There are various methods of applying the guide marks in the form of dots, and one of them is a method of applying a resin-made blind road to a substrate with an adhesive. The construction method does not need to select a substrate, so that the construction is easy, and only needs to paste the formed resin blind road on the site, so that the construction method has the characteristic of construction in a short time.
The resin-made blind road sticker is formed by kneading an acrylic resin liquid and a peroxide, an aggregate, a pigment, etc. as a curing agent, and then molding the mixture in a mold. As the acrylic resin solution, acrylic resin syrup obtained by dissolving an acrylic polymer in an acrylic monomer and adding a tertiary amine as a redox polymerization catalyst and dibenzoyl peroxide as a curing agent is often used. For example, patent document 1 describes that a resin sheet formed by using an acrylic resin paste to which a specific polyfunctional monomer is added is suitable for use as a blind road sticker because it can be firmly attached to a paved surface with a suitable size without using a mold at a construction site.
Documents of the prior art
Patent document
[ patent document 1 ] Japanese patent laid-open No. 2012-97561
Disclosure of Invention
However, the blind road sticker disclosed in patent document 1 is hard in resin used, and therefore loses flexibility when the temperature drops, and is difficult to stick to a base. In order to be easily attached to a base, it is necessary to perform a treatment such as blind road attachment heating, and workability is deteriorated. Further, if the blind road sticker disclosed in patent document 1 is to be attached to a substrate with difficulty, the blind road sticker may be cracked due to insufficient elongation.
Further, the resin composition for a blind road patch disclosed in patent document 1 has a problem that handling is difficult when forming into a shape of a blind road patch because of its high viscosity.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a blind patch having low hardness and excellent strength and elongation, and a curable resin composition for blind patches which can produce such a blind patch. Further, another object is to provide a resin composition for a blind road patch having a viscosity suitable for molding a resin blind road patch, and a method for producing a blind road patch using the resin composition for a blind road patch.
The above object is achieved by any one of the following inventions [ 1 ] to [ 20 ].
[ 1 ] A curable resin composition for a blind road sticker, which is a sheet-like cured product for evaluation, which is produced by the following method, and which has a hardness of D15-D65, a tensile strength of 5-50 MPa, and an elongation at break of 120-1000% when evaluated.
(method of producing a sheet-like cured product for evaluation)
The curable resin composition was vacuum defoamed, poured into a glass interlayer made of 2 glass plates covered with a PET film and a vinyl chloride gasket, and cured at 23 ℃ for 12 hours. After curing, the glass and PET films on both sides were removed to obtain a sheet-like cured product having a length of 250mm, a width of 250mm and a thickness of 3 mm.
(method of evaluating hardness)
2 pieces of the cured product in sheet form for evaluation having a thickness of 3mm were stacked to a thickness of 6mm, and the hardness at 23 ℃ was measured using a D type Shore durometer described in JIS K6253.
(method of evaluating tensile Strength and elongation at Break)
A dumbbell No. 3 described in JIS K6251 was punched out of a sheet-like cured product for evaluation having a thickness of 3mm, and a tensile test was conducted under conditions of an inter-chuck distance of 20mm and a tensile rate of 500mm/min to evaluate the tensile strength and elongation at break.
The curable resin composition for blind road application according to the above [ 1 ], wherein the curable resin composition for blind road application comprises: a (meth) acrylic polymer (A) containing a methyl methacrylate (a-1) unit and an alkyl (meth) acrylate (a-2) unit having an alkyl group with 2 to 20 carbon atoms, a methyl methacrylate (B), an alkyl (meth) acrylate (C) having an alkyl group with 2 to 20 carbon atoms, a polyfunctional (meth) acrylate (D), a reducing agent (E), and a curing agent (F).
The curable resin composition for a blind sidewalk application according to the above [ 2 ], wherein the total amount of the (meth) acrylic polymer (A), the methyl methacrylate (B) and the alkyl (meth) acrylate (C) is 100% by mass, the amount of the (meth) acrylic polymer (A) is 5 to 35% by mass, the amount of the methyl methacrylate (B) is 20 to 60% by mass, and the amount of the alkyl (meth) acrylate (C) is 20 to 60% by mass, and the amount of the polyfunctional (meth) acrylate (D) is 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of the (meth) acrylic polymer (A), the methyl methacrylate (B) and the alkyl (meth) acrylate (C).
[4 ] the curable resin composition for blind sidewalk application according to the above [ 2 ], wherein the content of the hydroxyalkyl (meth) acrylate (G) is 0 to 15% by mass in 100% by mass of the total amount of the curable resin composition for blind sidewalk application.
The curable resin composition for blind sidewalk application according to the above [ 2 ], wherein the polyfunctional (meth) acrylate (D) includes a di (meth) acrylate.
The curable resin composition for blind sidewalk application according to the above [ 5 ], wherein the polyfunctional (meth) acrylate (D) includes an alkoxylated bisphenol A di (meth) acrylate or a polyalkylene glycol di (meth) acrylate.
The curable resin composition for blind sidewalk application according to the above [ 6 ], wherein the polyfunctional (meth) acrylate (D) comprises ethoxylated bisphenol A di (meth) acrylate.
The curable resin composition for blind sidewalk application according to the above [ 2 ], wherein the (meth) acrylic polymer (A) contains: 5 to 95% by mass of methyl methacrylate (a-1) units, 5 to 95% by mass of alkyl (meth) acrylate (a-2) units having an alkyl group with 2 to 20 carbon atoms, and 0 to 20% by mass of radical polymerizable monomer (a-3) units other than (a-1) and (a-2).
The curable resin composition for a blind spot patch according to the above [ 2 ], wherein the alkyl (meth) acrylate (a-2) comprises n-butyl (meth) acrylate and/or 2-ethylhexyl (meth) acrylate.
The curable resin composition for a blind road sticker according to [ 2 ] above, wherein the alkyl (meth) acrylate (C) comprises n-butyl (meth) acrylate and/or 2-ethylhexyl (meth) acrylate.
[ 11 ] A resin composition for a blind sidewalk patch, comprising: a (meth) acrylic polymer (A), methyl methacrylate (B), an alkyl (meth) acrylate (C) having an alkyl group with 2 to 20 carbon atoms, a polyfunctional (meth) acrylate (D), and a reducing agent (E); the (meth) acrylic polymer (A) contains a methyl methacrylate (a-1) unit and an alkyl (meth) acrylate (a-2) unit having an alkyl group with 2-20 carbon atoms.
The resin composition for blind road application according to the above [ 11 ], wherein the viscosity of the resin composition for blind road application measured by a B-type viscometer at 23 ℃ is in the range of 2 to 1000 mPas.
The resin composition for a blind sidewalk application according to the above [ 11 ], wherein the total amount of the (meth) acrylic polymer (A), the methyl methacrylate (B) and the alkyl (meth) acrylate (C) is 100% by mass, the amount of the (meth) acrylic polymer (A) is 5 to 35% by mass, the amount of the methyl methacrylate (B) is 20 to 60% by mass, and the amount of the alkyl (meth) acrylate (C) is 20 to 60% by mass, and the amount of the polyfunctional (meth) acrylate (D) is 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of the (meth) acrylic polymer (A), the methyl methacrylate (B) and the alkyl (meth) acrylate (C).
[ 14 ] the resin composition for blind sidewalk application according to the above [ 11 ], wherein the content of the hydroxyalkyl (meth) acrylate (G) is 0 to 15% by mass in 100% by mass of the total amount of the curable resin composition for blind sidewalk application.
[ 15 ] the resin composition for a blind road sticker according to [ 11 ] above, wherein the polyfunctional (meth) acrylate (D) comprises a di (meth) acrylate.
[ 16 ] the resin composition for a blind road application according to [ 11 ] above, wherein the (meth) acrylic polymer (A) contains: 5 to 95% by mass of methyl methacrylate (a-1) units, 5 to 95% by mass of alkyl (meth) acrylate (a-2) units having an alkyl group with 2 to 20 carbon atoms, and 0 to 20% by mass of radical polymerizable monomer (a-3) units other than (a-1) and (a-2).
The resin composition for a blind road sticker according to [ 11 ] above, wherein the alkyl (meth) acrylate (a-2) comprises n-butyl (meth) acrylate and/or 2-ethylhexyl (meth) acrylate.
The resin composition for a blind road sticker according to [ 11 ] above, wherein the alkyl (meth) acrylate (C) comprises n-butyl (meth) acrylate and/or 2-ethylhexyl (meth) acrylate.
[ 19 ] A blind path paste comprising a cured product of the curable resin composition for a blind path paste according to any one of [ 1 ] to [ 10 ] above.
A method for producing a blind sidewalk paste according to any one of [ 11 ] to [ 18 ] above, wherein a mixture obtained by mixing the resin composition for a blind sidewalk paste, the curing agent (F), the aggregate and the pigment is cured into a shape of a blind sidewalk paste.
According to the present invention, a blind road sticker having low hardness and excellent strength and elongation and a curable resin composition for blind road stickers capable of producing such blind road stickers can be provided. Further, a resin composition for a blind road patch having a viscosity suitable for molding a resin blind road patch, and a method for producing a blind road patch using the resin composition for a blind road patch can be provided.
Detailed Description
The present invention is described in detail below. In the present invention, "methacrylic acid" is a generic term of "acrylic acid" and "methacrylic acid". "(meth) acrylate" refers to the generic term "acrylate" and "methacrylate". "(meth) acryloyl" is a generic term for "acryloyl" and "methacryloyl", having the formula: CH (CH)2(R) -C (═ O) - [ R represents a hydrogen atom or a methyl group]And (4) showing.
The curable resin composition for a blind road sticker of the present invention is a sheet-like cured product for evaluation, which is produced by the following method, and which has a hardness of D15 to D65, a tensile strength of 5 to 50MPa, and an elongation at break of 120 to 1000%. Hereinafter, the curable resin composition for blind via application will be simply referred to as a curable resin composition.
(method of producing a sheet-like cured product for evaluation)
The curable resin composition was vacuum defoamed, poured into a glass interlayer made of 2 glass plates covered with a PET film and a vinyl chloride gasket, and cured at 23 ℃ for 12 hours. After curing, the glass and PET films on both sides were removed to obtain a sheet-like cured product having a length of 250mm, a width of 250mm and a thickness of 3 mm.
(method of evaluating hardness)
2 pieces of the cured product in sheet form for evaluation having a thickness of 3mm were stacked to a thickness of 6mm, and the hardness at 23 ℃ was measured using a D type Shore durometer described in JIS K6253.
(method of evaluating tensile Strength and elongation at Break)
A dumbbell No. 3 described in JIS K6251 was punched out of a sheet-like cured product for evaluation having a thickness of 3mm, and a tensile test was conducted at a distance of 20mm between chucks and a tensile rate of 500mm/min to evaluate the tensile strength and elongation at break.
The curable resin composition contains: the (meth) acrylic polymer (A) containing a methyl methacrylate (a-1) unit and an alkyl (meth) acrylate (a-2) unit having an alkyl group with 2 to 20 carbon atoms, the methyl methacrylate (B), the alkyl (meth) acrylate (C) having an alkyl group with 2 to 20 carbon atoms, the polyfunctional (meth) acrylate (D), the reducing agent (E), and the curing agent (F) are preferable.
The resin composition for a blind road patch of the present invention comprises: a (meth) acrylic polymer (A) containing a methyl methacrylate (a-1) unit and an alkyl (meth) acrylate (a-2) unit having an alkyl group with 2 to 20 carbon atoms, a methyl methacrylate (B), an alkyl (meth) acrylate (C) having an alkyl group with 2 to 20 carbon atoms, a polyfunctional (meth) acrylate (D), and a reducing agent (E). Hereinafter, the resin composition for blind road patches is simply referred to as a resin composition. The viscosity of the resin composition measured by a B-type viscometer at 23 ℃ is preferably in the range of 2 to 800 mPas.
Hereinafter, the (meth) acrylic polymer (a), the methyl methacrylate (B), the alkyl (meth) acrylate (C) having 2 to 20 carbon atoms, the polyfunctional (meth) acrylate (D), the reducing agent (E), and the curing agent (F) may be referred to as a component (a), a component (B), a component (C), a component (D), a component (E), and a component (F), respectively. Methyl methacrylate (a-1), alkyl (meth) acrylate (a-2) in which the alkyl group has 2 to 20 carbon atoms, and a radically polymerizable monomer (a-3) other than (a-1) and (a-2) may be referred to as a monomer (a-1), a monomer (a-2), and a monomer (a-3), respectively. The unit of the monomer (a-1) is a structural unit derived from the monomer (a-1) in the polymer, and the unit of the monomer (a-2) and the unit of the monomer (a-3) are also the same.
[ (A) component ]
(A) The component (B) is preferably a (meth) acrylic polymer containing 5 to 95 mass% of the monomer (a-1) unit, 5 to 95 mass% of the monomer (a-2) unit, and 0 to 20 mass% of the monomer (a-3) unit. (A) The component (B) has the effect of adjusting the viscosity of the curable resin composition to a value suitable for molding and making the blind road adhesive have low hardness and high elongation. (A) The components can be used alone in1 kind, or can be used in combination in more than 2 kinds.
Specific examples of the monomer (a-2) include the following: ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and the like. These (a-2) components can be used alone in1 kind, or can be used in combination of 2 or more.
Specific examples of the monomer (a-3) include (meth) acrylic acid monomers having a carboxyl group such as 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxyethyl hexahydrophthalate, (meth) acrylic acid monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate, (meth) acrylic acid monomers having an alicyclic structure such as cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate and adamantyl (meth) acrylate, (meth) acrylic acid monomers having an alicyclic structure such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxy (meth) acrylate, and (meth) acrylic acid esters such as (meth) acrylic acid monomers containing a glycidyl (meth) acrylate, 2- (meth) acrylic acid ester, 2-glycidyl (meth) acrylate, 2-acryloyloxyethyl) acrylate, and (meth) acrylic acid (meth) acrylate, and (meth) acrylic acid (meth) acrylate containing a) acrylic acid ester such as acrylic acid ester, 2-glycidyl (meth) acrylate, 2-acrylic acid ester, 2-glycidyl (meth) acrylate, 2-acrylic acid ester, and (meth) acrylate, 2-acrylic acid ester, and (meth) acrylate, 2-acrylic acid ester, and (meth) acrylate, 2-acrylic acid.
The monomer (a-2) is preferably an alkyl (meth) acrylate having an alkyl group with 3 to 10 carbon atoms from the viewpoint of high elongation of the blind patch, and particularly preferably n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate from the viewpoint of high strength of the blind patch.
(A) The content of the monomer (a-1) unit in the component (A) is 5 to 95% by mass, preferably 15 to 85% by mass, and more preferably 25 to 75% by mass. The greater the content of the monomer (a-1) unit, the higher the strength of the blind road patch. The smaller the content of the monomer (a-1) unit, the lower the hardness and the higher the elongation of the blind via patch.
(A) The content of the monomer (a-2) unit in the component (a) is 5 to 95% by mass, preferably 15 to 85% by mass, and more preferably 25 to 75% by mass. The greater the content of the monomer (a-2) unit, the lower the hardness and the higher the elongation of the blind road patch. The smaller the content of the monomer (a-2) unit, the higher the strength of the blind road patch.
(A) The content of the monomer (a-3) unit in the component (a) is 0 to 20% by mass, preferably 0 to 10% by mass, and more preferably 0 to 5% by mass. The strength, elongation, hardness and other properties of the blind patch can be adjusted by the monomer (a-3) unit, but the compatibility of the component (a) with the components (B) and (C) is lowered as the content of the monomer (a-3) unit is increased.
(A) The mass average molecular weight of the component (A) is not particularly limited, but is preferably 1,000 to 300,000, more preferably 5,000 to 200,000, and still more preferably 10,000 to 150,000. When the mass average molecular weight is within the above range, the viscosity of the curable resin composition and the resin composition is low, and therefore the composition is likely to flow into a mold, and the moldability is improved.
(A) The glass transition temperature of the component (A) is not particularly limited, but is preferably 30 to 100 ℃, more preferably 35 to 90 ℃, and still more preferably 40 to 80 ℃. The higher the glass transition temperature, the higher the strength of the cured product can be. The lower the glass transition temperature, the lower the hardness and the higher the elongation of the blind road patch.
The content of the component (A) is preferably 5 to 35% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass, based on 100% by mass of the total amount of the components (A), (B), and (C). (A) The higher the content of the component(s), the higher the viscosity of the curable resin composition and the resin composition, and hence the prevention of the sedimentation of the aggregate. (A) The smaller the content of the component, the higher the elongation of the blind road patch.
The polymerization method for obtaining the component (a) is not particularly limited, and polymerization can be carried out by a known method such as solution polymerization, suspension polymerization, emulsion polymerization, partial polymerization, or the like. In the present invention, the suspension polymerization method is preferred because the control of the polymerization reaction and the separation of the produced polymer are relatively easy.
[ (B) component ]
(B) Methyl methacrylate as a component (B) has the effect of adjusting the viscosity of the curable resin composition and the viscosity of the resin composition to a value suitable for molding and improving the blind road adhesion strength. The content of the component (B) is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, and still more preferably 30 to 50% by mass, based on 100% by mass of the total amount of the components (A), (B) and (C). (B) The more the content of the components, the higher the strength of the blind road sticker. (B) The less the content of the components, the lower the hardness of the blind road sticker can be achieved.
[ (C) component ]
(C) The component (A) is an alkyl (meth) acrylate having an alkyl group with 2 to 20 carbon atoms. (C) The component (A) has the effect of adjusting the viscosity of the curable resin composition and the resin composition to a value suitable for molding and making the blind road adhesive have low hardness.
Specific examples of the component (C) include the following: ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and the like. These (C) components can be used alone in1 kind, also can be combined with 2 or more.
The component (C) is preferably an alkyl (meth) acrylate having an alkyl group with 3 to 10 carbon atoms from the viewpoint of increasing the elongation of the blind patch, and particularly preferably n-butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate from the viewpoint of increasing the strength of the cured product.
The content of the component (C) is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, and still more preferably 30 to 50% by mass, based on 100% by mass of the total amount of the components (A), (B), and (C). (C) The more the content of the components, the lower the hardness of the blind road paste. (C) The less the content of the components, the higher the strength of the blind road sticker.
[ (D) component ]
(D) The component (A) polyfunctional (meth) acrylate has the effect of improving the productivity of a cured product and enhancing the blind road adhesion strength by shortening the gelation time of the curable resin composition.
Specific examples of the component (D) include the following: alkylene glycol di (meth) acrylates (e.g., ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 3-butylene glycol di (meth) acrylate, 1, 4-butylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like); polyalkylene glycol di (meth) acrylates (e.g., diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dibutylene glycol di (meth) acrylate, tributylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and the like); alkoxylated bisphenol a di (meth) acrylates (e.g., bisphenol a ethylene oxide adduct di (meth) acrylate, bisphenol a propylene oxide adduct di (meth) acrylate, etc.); tricyclodecane dimethanol di (meth) acrylate; polycarbonate diol di (meth) acrylate; polyester diol di (meth) acrylate; difunctional (meth) acrylates such as urethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate; ethoxylated isocyanic acid tri (meth) acrylate; and a trifunctional (meth) acrylate such as an epsilon-caprolactone-modified tris ((meth) acryloyloxyethyl) isocyanurate, a tetrafunctional (meth) acrylate such as ditrimethylolpropane tetra (meth) acrylate, a pentafunctional (meth) acrylate such as dipentaerythritol penta (meth) acrylate, and a hexafunctional (meth) acrylate such as dipentaerythritol hexa (meth) acrylate. These (D) components may be used alone in1 kind, or may be used in combination in 2 or more kinds.
The component (D) is more preferably a bifunctional (meth) acrylate in view of ensuring a longer gelation time and a sufficient time for performing operations such as stirring and injection of the curable resin composition. In addition, as the component (D), alkoxylated bisphenol a di (meth) acrylate and polyalkylene glycol di (meth) acrylate are more preferable, and ethoxylated bisphenol a di (meth) acrylate is particularly preferable, from the viewpoint of making the blind road patch low in hardness, high in strength, and high in elongation.
The content of the component (D) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 1 to 10 parts by mass, per 100 parts by mass of the total amount of the components (A), (B) and (C). (D) The higher the content of the component (A), the higher the strength of the ethoxylated bisphenol A di (meth) acrylate. (D) The smaller the content of the component (A), the higher the elongation of the ethoxylated bisphenol A di (meth) acrylate can be obtained.
[ (E) component and (F) component ]
The curable resin composition of the present invention is cured by a polymerization reaction of radicals generated by the redox polymerization initiator. The redox polymerization initiator is a polymerization initiator used in combination of the reducing agent of the component (E) and the curing agent of the component (F). Examples of the combination of the component (E) and the component (F) which can be used in the redox polymerization initiator include the following components (1) to (4).
(1) A combination of an aromatic tertiary amine of the component (E) and dibenzoyl peroxide of the component (F).
Examples of the aromatic tertiary amines include the following: n, N-dimethyl-p-toluidine, N-diethylaniline, N-diethyl-p-toluidine, N- (2-hydroxyethyl) N-methyl-p-toluidine, N-bis (2-hydroxyethyl) -p-toluidine, N-bis (2-hydroxypropyl) -p-toluidine; ethylene oxide or propylene oxide adducts of N, N-bis (2-hydroxyethyl) -p-toluidine or N, N-bis (2-hydroxypropyl) -p-toluidine, and the like. These aromatic tertiary amines are not limited to p (para) isomers, and may be o (ortho) isomers or m (meta) isomers.
(2) A combination of a metal soap of the component (E) and a hydroperoxide of the component (F).
Specific examples of the metal soap include the following: cobalt naphthenate, copper naphthenate, manganese naphthenate, cobalt octylate, nickel octylate, cobalt acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, iron acetylacetonate, vanadyl acetylacetonate, vanadium acetylacetonate, and the like. Specific examples of the hydroperoxide include the following: cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide, t-butyl hydroperoxide, t-hexyl hydroperoxide, t-amyl hydroperoxide, 2, 5-dimethylhexane-2, 5-dihydroperoxide and the like.
(3) A combination of a thiourea compound of the component (E) and a hydroperoxide of the component (F).
Specific examples of the thiourea compound include the following: thiourea, ethylenethiourea, N '-dimethylthiourea, N' -diethylthiourea, N '-dipropylthiourea, N' -di-N-butylthiourea, N '-dilaurylthiourea, N' -diphenylthiourea, trimethylthiourea, 1-acetyl-2-thiourea, 1-benzoyl-2-thiourea and the like.
(4) A combination of a thiourea compound of the component (E) and a monocarbonate type peroxide of the component (F).
Specific examples of the monocarbonate type peroxide include the following: t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, allylt-butylperoxycarbonate, 1, 6-bis (t-butylperoxycarbonyloxy) hexane, and the like.
These components (E) and (F) may be used alone in1 kind, or may be used in combination in 2 or more kinds.
From the viewpoint of shortening the gelation time of the curable resin composition and improving the productivity, "(1) a combination of an aromatic tertiary amine and dibenzoyl peroxide" is particularly preferable. The aromatic tertiary amines are particularly preferably N, N-dimethyl-p-toluidine, N-diethyl-p-toluidine, N-bis (2-hydroxyethyl) -p-toluidine, and N, N-bis (2-hydroxypropyl) -p-toluidine from the viewpoint of giving a cured product having high strength and high elongation.
The content of the component (E) in the curable resin composition is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and still more preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the total amount of the components (A), (B), and (C). (E) Since the curing property becomes good as the content of the component is larger, the blind patch can have high strength and high elongation. (E) The smaller the content of the component(s), the longer the gelling time, and the easier the work such as stirring and injection of the curable resin composition can be performed.
The content of the component (F) in the curable resin composition is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and still more preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the total amount of the components (A), (B), and (C). (F) Since the curing property becomes good as the content of the component is larger, the blind patch can have high strength and high elongation. (F) The smaller the content of the component(s), the longer the gelling time, and the easier the work such as stirring and injection of the curable resin composition can be performed.
The curable resin composition of the present invention may contain hydroxyalkyl (meth) acrylate (G) as the polymerizable monomer other than the components (B), (C) and (D). The hydroxyalkyl (meth) acrylate (G) may be referred to as a component (G) hereinafter. The hardness may be adjusted in some cases by containing the component (G) in the curable resin composition.
Specific examples of the component (G) include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate. (G) The components can be used alone in1 kind, or can be used in combination in more than 2 kinds.
The content of the component (G) is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less, based on 100% by mass of the total amount of the curable resin composition. As described above, although the hardness of the curable resin composition can be further adjusted in some cases by containing the component (G), the hardness of the cured product tends to be higher as the content of the component (G) is larger.
[ other radically polymerizable monomers ]
The curable resin composition of the present invention may contain another radically polymerizable monomer (H) as a polymerizable monomer other than the components (B), (C), (D), and (G). Hereinafter, the other radical polymerizable monomer (H) may be referred to as a component (H). The curable resin composition may further have a viscosity and hardness adjusted by containing the component (H).
Specific examples of the component (H) include 1 type of the component (H) alone or 2 or more types of the component (H) in combination, for example, (meth) acrylic polymerizable monomers other than the components (B), (C), (D) and (G), aromatic vinyl monomers such as styrene and α -methylstyrene, vinyl cyanide monomers such as acrylonitrile, and vinyl ester monomers such as vinyl acetate.
Specific examples of the (meth) acrylic polymerizable monomer other than the components (B), (C), (D), and (G) include the following: (meth) acrylic acid monomers having a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, and 2- (meth) acryloyloxyethyl hexahydrophthalate; alicyclic structure-containing (meth) acrylic monomers such as cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and adamantyl (meth) acrylate; (meth) acrylic monomers having an aromatic ring structure such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, phenyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, phenylbenzyl (meth) acrylate, naphthyl (meth) acrylate, and (1-naphthyl) meth (meth) acrylate; alkoxy (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and butoxyethyl (meth) acrylate; (meth) acrylic acid monomers having a heterocyclic structure such as tetrahydrofuran (meth) acrylate and glycidyl (meth) acrylate; 2- (meth) acryloyloxyethyl acid phosphorus, trifluoroethyl (meth) acrylate, perfluorodecyl (meth) acrylate, and (meth) acryloylmorpholine, and these (meth) acrylic polymerizable monomers may be used alone in1 kind or in combination of 2 or more kinds.
The content of the component (H) is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less, based on 100% by mass of the total amount of the curable resin composition. As described above, although the viscosity and hardness of the curable resin composition can be further adjusted in some cases by containing the component (H), the elongation of the cured product tends to decrease as the content of the component (H) increases. When the content of the component (H) is 15% by mass or less in 100% by mass of the total amount of the curable resin composition, the viscosity of the curable resin composition and the hardness of the cured product can be adjusted while maintaining the elongation of the cured product.
[ other Components ]
The curable resin composition of the present invention may contain a component (I) other than the components (a), (B), (C), (D), (E), (F), (G) and (H) as long as the effects of the present invention are not impaired. Hereinafter, the other component (I) may be referred to as component (I).
Examples of the component (I) include various additives such as paraffin, rubber, antioxidant, plasticizer, ultraviolet absorber, thixotropic agent, defoaming agent, polymerization inhibitor, silane coupling agent, and the like; and radical polymerization initiators such as thermal polymerization initiators and photopolymerization initiators.
In the curable resin composition of the present invention, paraffin may be added to suppress inhibition of curing by oxygen. It is preferable to use 2 or more kinds of paraffins having different melting points in combination. The melting point of the paraffin is preferably 40-80 ℃. Specific examples of the paraffin include the following: paraffin 115 (melting point: 47 ℃ C. in the product catalog, manufactured by Nippon wax Co., Ltd.), Paraffin130 (melting point: 55 ℃ C. in the product catalog, manufactured by Nippon wax Co., Ltd.), Paraffin 150 (melting point: 66 ℃ C. in the product catalog, manufactured by Nippon wax Co., Ltd.), and the like. When the melting point is 40 ℃ or higher, a sufficient air barrier effect can be obtained when the resin composition is cured, and the surface curability is good. On the other hand, when the melting point is 80 ℃ or lower, the solubility of paraffin in the resin composition becomes good when the resin composition is prepared. Further, by using paraffins having different melting points in combination, a sufficient air-shielding effect can be obtained even when the temperature is changed, and the surface curability is improved. When used in combination, the difference in melting point is preferably about 5 to 20 ℃. As the paraffin, paraffin dispersed in an organic solvent may be used from the viewpoint of improving surface curability. The air shielding effect can be effectively exhibited by making the paraffin wax be in a dispersed state in the organic solvent, and making the particle diameter of the paraffin wax in the dispersed state be 0.1-50 μm. Paraffin wax in a dispersed state is commercially available, and may be added directly.
In the curable resin composition of the present invention, rubber may be added to improve the strength and elongation of the blind patch. Specific examples of the rubber include the following: a (meth) acrylate-butadiene copolymer, a (meth) acrylate-butadiene-styrene copolymer, polybutadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber, and the like.
Specific examples of the antioxidant include stearyl 3- (3 ', 5' -di-t-butyl-4 '-hydroxyphenyl) propionate, tetrakis- [ methylene-3- (3', 5 '-di-t-butyl-4' -hydroxyphenyl) propionate ] methane, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], phosphorus antioxidants such as triphenyl phosphite, triisodecyl phosphite, tridecyl phosphite, and tris (2, 4-di-t-butylphenyl) phosphite, and phosphorus antioxidants such as dihexyl sulfide, dilauryl 3,3 '-thiodipropionate, ditridecyl 3, 3' -thiodipropionate, and tetralauryl thiopropionate (β -thiopropionate).
In the curable resin composition of the present invention, a plasticizer may be added to reduce the hardness of the blind via patch. Specific examples of the plasticizer include the following: phthalate esters such as dibutyl phthalate, di (2-ethylhexyl) phthalate and diisodecyl phthalate, adipate esters such as di (2-ethylhexyl) adipate and octyl adipate, sebacate esters such as dibutyl sebacate and di (2-ethylhexyl) sebacate, dibasic fatty acid esters such as di (2-ethylhexyl) azelate and azelate esters such as octyl azelate; paraffins such as chlorinated paraffin, and the like.
In the curable resin composition of the present invention, an ultraviolet absorber may be added to suppress the photo-aging of the blind patch. Specific examples of the ultraviolet absorber include the following: 2-hydroxybenzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4, 4 ' -dimethoxybenzophenone and 2-hydroxy-4, 4 ' -dibutoxybenzophenone, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) benzotriazole or a halide thereof, phenyl salicylate and p-tert-butyl salicylate.
In the curable resin composition of the present invention, a thixotropic agent may be added to suppress the sedimentation of the aggregate to be added. Specific examples of the thixotropic agent include organic thixotropic agents such as urethane urea, fatty acid amide, organic bentonite, oxidized polyethylene wax and organically modified sepiolite, and inorganic thixotropic agents such as fine silica particles.
In the curable resin composition and the resin composition of the present invention, a defoaming agent may be added for removing bubbles. Specific examples of the defoaming agent include an acrylic defoaming agent in which a specific acrylic polymer is dissolved in a solvent, and a vinyl defoaming agent in which a specific vinyl polymer is dissolved in a solvent. Specific product names of the defoaming agent include, for example, the following: DISPARLON series (product names: OX-880EF, OX-881, OX-883, OX-77EF, OX-710, OX-8040, 1922, 1927, 1950, P-410EF, P-420, P-425, PD-7, 1970, 230HF, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, etc.) manufactured by Nanguo Kan, etc. and BYK-052, BYK-1752, etc. manufactured by BYK Japan.
In the resin composition of the present invention, a polymerization inhibitor may be added for the purpose of improving storage stability. Specific examples of the polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2, 6-di-t-butyl-4-methylphenol.
In the curable resin composition of the present invention, a silane coupling agent may be added to improve the adhesion between the aggregate and other components. Specific examples of the silane coupling agent include the following: 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (glycidyloxypropyl) trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like.
In the curable resin composition of the present invention, a thermal polymerization initiator may be added to improve curability. Specific examples of the thermal polymerization initiator include the following: ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) cyclohexane, and 1, 1-bis (t-butylperoxy) cyclohexane; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diacyl peroxides such as dilauroyl peroxide; peroxydicarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate and bis (2-ethylhexyl) peroxydicarbonate; peroxides such as peroxy esters such as t-butyl peroxy-2-ethylhexanoate, t-hexylperoxy isopropyl monocarbonate, t-butyl peroxybenzoate, and 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate; azo compounds such as 2,2 ' -azobis (isobutyronitrile), 2 ' -azobis (2-methylbutyronitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 1 ' -azobis-1-cyclohexanecarbonitrile, dimethyl-2, 2 ' -azobisisobutyl ester, 4 ' -azobis-4-cyanovaleric acid, and 2,2 ' -azobis- (2-amidinopropane) dihydrochloride.
In the curable resin composition of the present invention, a photopolymerization initiator may be added to improve curability. Specific examples of the photopolymerization initiator include the following: benzophenone type compounds such as benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, methyl benzoylbenzoate and 4-phenylbenzophenone; anthraquinone compounds such as t-butylanthraquinone and 2-ethylanthraquinone; alkylphenol type compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo { 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] acetone }, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, 2-methyl- [4- (methylthio) phenyl ] -2-morpholinyl-1-one, and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one; thioxanthone-type compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, diethylthioxanthone, isopropylthioxanthone and the like; acylphosphine oxide type compounds such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide and phenylbis (2,4, 6-trimethylbenzoyl) -phosphine oxide; and phenylglyoxylic acid type compounds such as methyl phenylglyoxylate.
< method for producing curable resin composition >
It is preferable to add components other than the component (F) to prepare a resin composition in the form of a slurry, and to add the component (F) to the resin composition immediately before the curing reaction proceeds.
Examples of the method of adding the resin composition include a method of stirring and mixing at normal temperature, a method of heating and mixing them, and the like. When the addition is carried out by heating, the compatibility becomes good, and from the viewpoint of enabling more uniform mixing, the mixing is preferably carried out at 40 to 100 ℃, and the stirring time for the mixing is preferably 0.1 to 5 hours. When preparing the resin composition, the components (G), (H) and (I) may be added as required.
< viscosity of resin composition >
The viscosity of the resin composition containing the component (F) without the curing agent is preferably within a range of 2 to 1,000 mPas, more preferably 3 to 500 mPas, and further preferably 5 to 300 mPas as measured at 23 ℃ with a B-type viscometer. When the viscosity of the curable resin composition is within the above range, the aggregate is prevented from settling, and the composition can easily flow into a mold.
< gelation time of curable resin composition >
The gelling time of the curable resin composition is preferably 3 to 45 minutes, more preferably 5 to 40 minutes, and still more preferably 8 to 35 minutes, from the time when the component (F) is added to the slurry mixture to which the component (F) other than the component (F) is added at 23 ℃. When the gelation time of the curable resin composition is within the above range, productivity and handling properties are improved.
Hardness of cured product
In the curable resin composition of the present invention, when 2 sheets of a sheet-like cured product for evaluation having a thickness of 3mm prepared by the following method are stacked to have a thickness of 6mm and the hardness at 23 ℃ is measured using a shore D hardness meter according to JIS K6253, the hardness of the cured product is preferably D15 to D65, more preferably D25 to D60, and still more preferably D30 to D55. Within the above range, the blind road sticker has hardness that the blind road stickers are not stuck to each other and flexibility that the blind road sticker is not deformed at a low temperature.
A sheet-like cured product for evaluation was produced by the following method. The curable resin composition was vacuum defoamed, poured into a glass interlayer made of 2 glass plates covered with a PET film and a vinyl chloride gasket, and cured at 23 ℃ for 12 hours. After curing, the glass and PET films on both sides were removed to obtain a sheet-like cured product for evaluation having a length of 250mm, a width of 250mm and a thickness of 3 mm.
< tensile Strength and elongation at Break of cured product >
The curable resin composition of the present invention was obtained by stamping a dumbbell shape No. 3 described in JISK6251 from the above-mentioned sheet-like cured product for evaluation having a thickness of 3mm, and the thickness was measured by "distance between chucks: 20mm, drawing speed: 500mm/min. "the tensile strength in the tensile test is preferably 5MPa or more, more preferably 7MPa or more, and further preferably 9MPa or more. When the tensile strength of the evaluation method is 5MPa or more, the blind via patch produced from the curable resin composition can suppress problems such as cracking during actual use. The tensile strength is preferably 50MPa or less, and burrs of the blind road patch can be easily removed.
The elongation at break in the tensile test is preferably 120% or more, more preferably 160% or more, and still more preferably 190% or more. When the elongation at break is 120% or more, the blind via produced from the curable resin composition can be prevented from cracking when it is stuck to a substrate. The elongation at break is preferably 1000% or less, and burrs of the blind road tape can be easily removed.
< action Effect >
The above-described cured sheet for evaluation is produced, and the curable resin composition for a blind road patch of the present invention, which has a hardness of D15 to D65, a tensile strength of 5 to 50MPa, and an elongation at break of 120 to 1000%, is evaluated, can provide a blind road patch having excellent workability. The resin composition for a blind road patch of the present invention containing (a), (B), (C), (D) and (E) has a viscosity suitable for molding and therefore is excellent in workability during molding.
[ Blind road label ]
The blind via patch of the present invention is obtained by curing the curable resin composition of the present invention in the shape of a blind via patch. The blind road patch preferably further contains an aggregate for the purpose of suppressing curing shrinkage during molding, improving strength, improving durability such as abrasion, and the like.
Specific examples of the aggregate include the following: sand, silica sand, river sand, gypsum rubrum, emery, marble, calcium carbonate, kaolin, bentonite, mica, talc, silicon carbide powder, silicon nitride powder, boron nitride powder, alumina, slag, glass powder, ceramic aggregate, pottery chips, coloring aggregate, and the like. These aggregates may be used alone in1 kind, or may be used in combination in 2 or more kinds.
The particle size of the aggregate is determined according to the thickness of the blind patch, but the screened particle size is preferably 5mm or less, more preferably 3mm or less, and still more preferably 2mm or less. When the particle size of the aggregate is 5mm or less, the blind road sticker can be made thin, and flexibility can be easily obtained. The particle size distribution of the aggregate is not particularly limited and may be appropriately adjusted because it is derived from the viscosity of the curable resin composition, the shape of the aggregate, the thickness of the molding blind patch, and the like.
The amount of the aggregate added is preferably 50 to 400 parts by mass, more preferably 75 to 350 parts by mass, and still more preferably 100 to 300 parts by mass, per 100 parts by mass of the curable resin composition. When the addition amount of the aggregate is 50 parts by mass or more, the strength and abrasion resistance of the blind road paste can be improved. When the amount of the aggregate is 400 parts by mass or less, the strength and wear resistance of the blind road patch can be improved, and cracks are less likely to occur.
The blind road sticker of the invention can be added with pigment for coloring. Examples of the pigment include organic pigments such as azo pigments and phthalocyanine pigments; ceramic pigments, inorganic pigments such as iron oxide and titanium oxide, and the like. These pigments may be used alone in1 kind, or may be used in combination in 2 or more kinds. The amount of the pigment added is preferably 0 to 40 parts by mass, more preferably 0.5 to 35 parts by mass, and still more preferably 1 to 30 parts by mass, per 100 parts by mass of the curable resin composition.
The method for manufacturing the blind road sticker is not particularly limited, and the following methods can be exemplified as a preferable manufacturing method: first, a resin composition to which components other than the component (F) are added is prepared, and after the aggregate and the pigment are added, the component (F) is added to obtain a curable resin composition. The obtained curable resin composition is poured into a mold made of polypropylene, silicon or the like during a gelation time, and then cured, and the mold is released after curing, thereby producing a blind patch. In order to reduce the bubbles in the blind via paste, vacuum defoaming, vibration defoaming, or the like may be performed before the blind via paste is poured into the mold. The curing temperature after flowing into the mold is preferably 5 to 65 ℃, more preferably 10 to 60 ℃, and further preferably 15 to 55 ℃. When the curing temperature is set to 5 to 65 ℃, the curing reaction of the curable resin composition is sufficiently performed, and the characteristics of the blind road sticker are improved. The curing time varies depending on the curing temperature, and is preferably 10 minutes to 24 hours. The resulting blind road patch may be laid by being adhered to a substrate such as a road surface with an adhesive.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "part" means "part by mass". Before the examples, various measuring methods and examples of producing a polymer will be described.
[ measurement method ]
< 1. determination of Mass average molecular weight >
The polymers 1 to 6 were dissolved in a solvent (tetrahydrofuran), respectively, and the molecular weights were measured by gel permeation chromatography. The mass average molecular weight was determined as a value of the measured molecular weight in terms of polystyrene.
< 2. measurement of glass transition temperature >
The glass transition temperatures of the polymers 1 to 6 were measured by a differential scanning calorimeter (DSC8230, Rigaku corporation).
< 3. measurement of viscosity >
The viscosity of the curable resin composition (slurry mixture) to which the components other than the component (F) of the curing agent were added was measured with a B-type viscometer at a liquid temperature of 23 ℃.
< 4. gelation time >
The time until the fluidity of the curable resin composition disappeared was measured at 23 ℃ from the time when the component (F) was added to the curable resin composition to which the components other than the component (F) were added, and this time was taken as the gelation time.
Hardness & lt 5 >
2 pieces of cured sheet materials having a thickness of 3mm were stacked to a thickness of 6mm, and the hardness at 23 ℃ was measured using a D type Shore hardness meter described in JIS K6253.
< 6 tensile Strength, elongation at Break >
A dumbbell No. 3 described in JIS K6251 was punched out from a sheet-like cured product having a thickness of 3mm, and the thickness was measured in terms of "distance between chucks: 20mm, drawing speed: 500mm/min. "tensile test was performed, and tensile strength and elongation at break were measured.
Production example 1 production of Polymer 1
145 parts of deionized water and 0.5 part of polyvinyl alcohol (saponification rate: 80%, polymerization degree: 1,700) as a dispersion stabilizer were charged into a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, and then stirred. After the polyvinyl alcohol was completely dissolved, the stirring was stopped, and 60 parts of methyl methacrylate, 40 parts of n-butyl methacrylate, 0.1 part of 2, 2' -azobis (isobutyronitrile), and 0.5 part of n-octylmercaptan were added and stirred again. The atmosphere in the polymerization apparatus was replaced with nitrogen under stirring, and the temperature was raised to 70 ℃ to carry out polymerization. After the exothermic peak of polymerization was detected, the temperature was raised to 98 ℃ and the reaction was continued for 0.5 hour, followed by cooling to 40 ℃. The resulting aqueous suspension was filtered through a nylon filter cloth having a pore size of 45 μm, and the filtrate was washed with deionized water. After dehydration, the resulting mixture was dried at 40 ℃ for 20 hours to obtain a granular (meth) acrylic polymer (hereinafter referred to as "polymer 1"). The mass average molecular weight (Mw) of the polymer 1 was 42,000, and the glass transition temperature (Tg) was 65 ℃.
Production examples 2 to 7 production of polymers 2 to 7
Polymers 2 to 6 were produced in the same manner as in production example 1 except that the kinds and the amounts of the raw materials used were changed to the conditions shown in Table 1, and the mass average molecular weights and the glass transition temperatures were measured. The details of the symbols and abbreviations in table 1 are shown in table 3.
[ TABLE 1 ]
[ example 1 ]
1. Production of curable resin composition
A reaction vessel equipped with a cooler was charged with 40 parts of methyl methacrylate as component (B), 40 parts of 2-ethylhexyl acrylate as component (C), 5 parts of ethoxylated bisphenol A diacrylate as component (D) (product name: New Frontier BPE-4 manufactured by first Industrial pharmaceutical Co., Ltd.), and 1 part of N, N-bis (2-hydroxyethyl) -p-toluidine (product name: PTEO manufactured by Nippon emulsifier Co., Ltd.). While these components in the reaction vessel were stirred, 20 parts of polymer 1 produced in production example 1 as component (a) was added. Subsequently, the solution in the reaction vessel was heated to 60 ℃ and stirred for 2 hours while maintaining the temperature. After confirming complete dissolution of the polymer 1, the mixture was cooled to obtain a slurry mixture.
To the resulting slurry mixture, 3 parts of (1.2 parts of) Nyper NS (suspension of dibenzoyl peroxide (purity: 40%) manufactured by nippon oil corporation, "trade name: Nyper NS") was added as a component (F), and the mixture was stirred to obtain a curable resin composition.
2. Production of cured sheet for evaluation
The curable resin composition was vacuum defoamed, poured into a glass interlayer made of 2 glass plates covered with a PET film and a vinyl chloride gasket, and cured at 23 ℃ for 12 hours. After curing, the glass and PET films on both sides were removed to obtain a sheet-like cured product for evaluation having a length of 250mm, a width of 250mm and a thickness of 3 mm.
3. Evaluation of
The viscosity of the slurry mixture was measured, the gelation time of the curable resin composition was measured, and the hardness, tensile strength, and elongation at break of the sheet-like cured product for evaluation were measured. The measurement results are shown in Table 2-1. Further, the details of the symbols and abbreviations in Table 2-1 are shown in tables 3 to 6.
[ examples 2 to 26 ]
Slurry mixtures, curable resin compositions, and evaluation sheet-like cured products were prepared and various measurements were performed in the same manner as in example 1, except that the formulation compositions shown in table 2-1 or table 2-2 were changed. The measurement results are shown in Table 2-1 or Table 2-2.
[ comparative examples 1 to 3 ]
A slurry mixture, a curable resin composition, and a cured product in sheet form for evaluation were prepared and various measurements were performed in the same manner as in example 1, except that the formulation compositions shown in tables 2 to 3 were changed. The results are shown in tables 2 to 3.
[ TABLE 2-1 ]
[ TABLE 2-2 ]
[ TABLE 2-3 ]
[ TABLE 3 ]
[ TABLE 4 ]
[ TABLE 5 ]
[ TABLE 6 ]
As is clear from the results in tables 2-1, 2-2 and 2-3, the curable resin compositions of the examples can give cured products having low hardness and excellent strength and elongation. On the other hand, the cured product of comparative example 1 obtained from the curable resin composition containing polymethyl methacrylate in place of the component (a) had high hardness and low elongation. The curable resin composition of comparative example 2, to which polymethyl methacrylate having a higher weight average molecular weight than that of comparative example 1 was added instead of component (a), had a high viscosity, and the hardness of the resulting cured product was high. The cured product of comparative example 3 obtained from the curable resin composition in which the component (B) in comparative example 1 was replaced with a plasticizer had a low elongation as in comparative example 1.
[ example 31 ]
1. Manufacture of blind road plaster
To 100 parts of the curable resin composition produced in example 1, 20 parts of aggregate A, 50 parts of aggregate C, 20 parts of aggregate D, 10 parts of aggregate E, 3 parts of colorant α and 2 parts of colorant β were added at 23 ℃ and mixed by stirring with a high-speed stirrer for 2 minutes (1000 rpm) to obtain a curable mixture, the curable mixture was poured into a warning mold having a length of 60cm, a width of 30cm and a thickness of 2mm, and then a defoaming treatment was performed with a shaker to coat a PET film on the upper surface of the warning mold and cure the curable mixture at 23 ℃ for 24 hours to suppress inhibition of oxygen curing, and the curable mixture was cured for 24 hours and then demolded to obtain a blind patch (60 cm in length, 30cm in width and 2mm in thickness).
2. Evaluation of flexibility
The blind sidewalk is placed on a flat table top at 23 ℃, one side of the blind sidewalk is fixed on the table by hands, and the side opposite to the fixed side is slowly lifted, so that the blind sidewalk is bent. Flexibility was evaluated according to the following criteria. The evaluation results are shown in Table 7. The details of the symbols and abbreviations in table 7 are shown in table 8.
○, the blind road sticker can be bent to more than 45 degrees without cracks by taking the table top as 0 degree.
X: the table top is 0 degrees, and the blind road sticker cannot be bent to more than 45 degrees without cracks.
[ examples 32 to 35 and comparative example 11 ]
A blind patch was produced in the same manner as in example 31 except that the formulation composition shown in table 7 was changed, and flexibility was evaluated. The results are shown in Table 7.
[ TABLE 7 ]
[ TABLE 8 ]
| Aggregate A | Ceramic sand, manufactured by bamboo-breaking mining company, "trade name; scherben B' |
| Aggregate B | Ceramic sand, manufactured by bamboo-breaking mining company, "trade name; scherben S-3L " |
| Aggregate C | Ceramic sand, manufactured by bamboo-breaking mining company, "trade name; scherben S-3' |
| Aggregate D | Silicon sand, manufactured by the company Sanhe salicide, "trade name; sanhe silica sand No. 7 " |
| Aggregate E | Ceramic sand, manufactured by bamboo-breaking mining company, "trade name; scherben powder " |
| Colorant α | Titanium oxide, trade name, manufactured by stone industries; titanium oxide WHITE product CR-90 " |
| Colorant β | Manufactured by LANXESS corporation, "trade name; bayferrox 920G " |
| Thickening agent | Organically modified sepiolite, manufactured by shiwa corporation, "trade name; AG-200 " |
From the results in Table 7, the blind road stickers of examples 31 to 35 using the curable resin compositions prepared in the examples exhibited good flexibility. On the other hand, the blind road sticker of comparative example 11 using the curable resin composition produced in comparative example was hard and could not be bent up to 45 °.
Claims (14)
1. A resin composition for a blind road sticker, wherein a sheet-like cured product for evaluation is produced by the following method, and the cured product is evaluated to have a hardness of D15-D65, a tensile strength of 5-50 MPa, and an elongation at break of 230-1000%;
the resin composition contains: a (meth) acrylic polymer (A), methyl methacrylate (B), an alkyl (meth) acrylate (C) having an alkyl group with 2 to 20 carbon atoms, and a polyfunctional (meth) acrylate (D); the (meth) acrylic polymer (A) contains a methyl methacrylate (a-1) unit and an alkyl (meth) acrylate (a-2) unit having an alkyl group with 2-20 carbon atoms;
method for producing evaluation-use sheet-like cured product:
mixing a curing agent with the resin composition, defoaming the mixture in vacuum, pouring the mixture into a glass interlayer made of 2 glass plates covered by a PET film and a sealing gasket made of vinyl chloride, curing the mixture at 23 ℃ for 12 hours, and removing the glass and the PET film on both sides after curing to obtain a sheet-shaped cured product with the longitudinal length of 250mm, the transverse length of 250mm and the thickness of 3 mm;
evaluation method of hardness:
2 pieces of the evaluation sheet-like cured product having a thickness of 3mm were stacked to a thickness of 6mm, and the hardness at 23 ℃ was measured using a D type Shore durometer described in JIS K6253;
evaluation methods of tensile strength and elongation at break:
a dumbbell No. 3 described in JIS K6251 was punched out of a sheet-like cured product for evaluation having a thickness of 3mm, and a tensile test was conducted under conditions of an inter-chuck distance of 20mm and a tensile rate of 500mm/min to evaluate the tensile strength and elongation at break.
2. The resin composition for blind sidewalk according to claim 1, wherein the resin composition contains a reducing agent (E).
3. The resin composition for a blind road sticker according to claim 1 or 2, wherein the polyfunctional (meth) acrylate (D) is 0.1 to 20 parts by mass relative to 100 parts by mass of the total amount of the (meth) acrylic polymer (A), the methyl methacrylate (B) and the alkyl (meth) acrylate (C), wherein the amount of the (meth) acrylic polymer (A) is 5 to 35% by mass, the amount of the methyl methacrylate (B) is 20 to 60% by mass, and the amount of the alkyl (meth) acrylate (C) is 20 to 60% by mass, based on 100 parts by mass of the total amount of the (meth) acrylic polymer (A), the methyl methacrylate (B) and the alkyl (meth) acrylate (C).
4. The resin composition for a blind road sticker according to claim 1 or 2, wherein the hydroxyalkyl (meth) acrylate (G) is contained in an amount of 0 to 15 mass% based on 100 mass% of the total amount of the resin composition.
5. The resin composition for blind road application according to claim 1 or 2, wherein a di (meth) acrylate is contained as the polyfunctional (meth) acrylate (D).
6. The resin composition for a blind road sticker according to claim 5, wherein the polyfunctional (meth) acrylate (D) comprises an alkoxylated bisphenol A di (meth) acrylate or a polyalkylene glycol di (meth) acrylate.
7. The resin composition for blind sidewalk according to claim 6, wherein the polyfunctional (meth) acrylate (D) comprises ethoxylated bisphenol A di (meth) acrylate.
8. The resin composition for blind road application according to claim 1 or 2, wherein the (meth) acrylic polymer (a) contains: 5 to 95% by mass of methyl methacrylate (a-1) units, 5 to 95% by mass of alkyl (meth) acrylate (a-2) units having an alkyl group with 2 to 20 carbon atoms, and 0 to 20% by mass of radical polymerizable monomer (a-3) units other than (a-1) and (a-2).
9. The resin composition for blind sidewalk according to claim 1 or 2, wherein the alkyl (meth) acrylate (a-2) comprises n-butyl (meth) acrylate and/or 2-ethylhexyl (meth) acrylate.
10. The resin composition for blind sidewalk according to claim 1 or 2, wherein the alkyl (meth) acrylate (C) comprises n-butyl (meth) acrylate and/or 2-ethylhexyl (meth) acrylate.
11. The resin composition for a blind road sticker according to claim 1 or 2, wherein the resin composition has a viscosity in the range of 2 to 1000 mPas at 23 ℃ as measured with a B-type viscometer.
12. A curable resin composition for a blind road sticker, comprising the resin composition for a blind road sticker according to any one of claims 1 to 11 and a curing agent (F).
13. A blind sidewalk patch comprising a cured product of the curable resin composition for a blind sidewalk patch according to claim 12.
14. A method for producing a blind sidewalk paste, comprising mixing 100 parts by mass of the curable resin composition for a blind sidewalk paste according to claim 12 with 50 to 400 parts by mass of an aggregate and 0.5 to 40 parts by mass of a pigment, and curing the mixture into a shape of a blind sidewalk paste.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1037904A (en) * | 1964-05-01 | 1966-08-03 | Du Pont | Polymerizable solutions of methyl methacrylate polymers in methyl methacrylate |
| TW404966B (en) * | 1995-10-17 | 2000-09-11 | Ici Acrylics Inc | Acrylic compositions |
| JP2010132876A (en) * | 2008-10-27 | 2010-06-17 | Mitsubishi Rayon Co Ltd | Curable (meth)acrylic resin composition, laminated material intermediate membrane, and laminated material |
| CN102933612A (en) * | 2010-06-10 | 2013-02-13 | 三菱丽阳株式会社 | Process for production of acrylic polymer, acrylic polymer obtained by the process, and plastisol composition using same |
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| JP2867086B2 (en) * | 1991-09-18 | 1999-03-08 | 三菱レイヨン株式会社 | Acrylic syrup composition |
| JP3330360B2 (en) * | 1999-12-08 | 2002-09-30 | ライン工業株式会社 | Plate and manufacturing method thereof |
| JP2005220670A (en) * | 2004-02-06 | 2005-08-18 | Junichi Yokoshima | Plate, manufacturing method thereof, and building |
| JPWO2013054896A1 (en) * | 2011-10-14 | 2015-03-30 | 三菱レイヨン株式会社 | Radical polymerization type acrylic resin composition, waterproofing material composition, laminate and method for producing the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1037904A (en) * | 1964-05-01 | 1966-08-03 | Du Pont | Polymerizable solutions of methyl methacrylate polymers in methyl methacrylate |
| TW404966B (en) * | 1995-10-17 | 2000-09-11 | Ici Acrylics Inc | Acrylic compositions |
| JP2010132876A (en) * | 2008-10-27 | 2010-06-17 | Mitsubishi Rayon Co Ltd | Curable (meth)acrylic resin composition, laminated material intermediate membrane, and laminated material |
| CN102933612A (en) * | 2010-06-10 | 2013-02-13 | 三菱丽阳株式会社 | Process for production of acrylic polymer, acrylic polymer obtained by the process, and plastisol composition using same |
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| JP2017101407A (en) | 2017-06-08 |
| CN106957392A (en) | 2017-07-18 |
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