CN107074998A - Polyester and resin composition - Google Patents
Polyester and resin composition Download PDFInfo
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- CN107074998A CN107074998A CN201580057523.2A CN201580057523A CN107074998A CN 107074998 A CN107074998 A CN 107074998A CN 201580057523 A CN201580057523 A CN 201580057523A CN 107074998 A CN107074998 A CN 107074998A
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
-
- 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
- C08F265/02—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 acids, salts or anhydrides
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
A kind of polyester and resin composition; it is characterized in that; it contains polyester resin (A), (methyl) acrylic acid series polymeric compounds (B), monomer (C) with (methyl) acryloyl group, organo-metallic compound (D), solvent (E) and selected from least one of oligomer and its hydrolysate containing fluoro-alkyl fluorochemical (F) shown in following formulas (1); according to the present invention it is possible to provide the transparency, adaptation and the excellent polyester and resin composition of soil resistance.In addition, according to the present invention it is possible to providing the transparency, adaptation, soil resistance, antibiotic property and the excellent polyester and resin composition of antiviral property.
Description
Technical field
The present invention relates to the top coat materials, clothes, fiber as automobile component, electronic instrument, building materials field etc. etc.
The useful transparency of surface finished materials, adaptation and the excellent polyester and resin composition of soil resistance, are further related to transparent, close
Conjunction property, soil resistance, antibiotic property and the excellent polyester and resin composition of antiviral property.
Background technology
In the decorative uses such as automobile component, electronic instrument, building materials field, because mouldability is excellent, cheap, light weight, because
This various built up membrane, various synthetic resin sheet materials are used as top coat materials.
But there is transparency reduction, the non-soil resistance caused by fingerprint adheres to, the adaptation etc. such as be easily peeled off and ask
Topic, in order to solve these various problems, it was also proposed that for film impart the soil resistance film of anti-pollution function (referring for example under
State patent document 1 and 2).
The special antireflection film for being attached to the element as optical articles, optical light filter, optical lens, liquid crystal display
The surface of the optical components such as device, CRT monitor, projection TV, plasma scope, EL display, wallpaper, billboard etc.
Dirt causes optical property, reduction attractive in appearance.
In addition, in recent years, the various electronic instruments of touch panel mode attract attention, but the touch for utilizing finger tip to operate
The display picture of panel generally adheres to the dirts such as the grease of finger, fingerprint and is difficult to see that the situation of display picture and increases.
Therefore, for top coat materials such as transparent and excellent soil resistance film, sheet materials, it is desirable to which its soil resistance is further carried
It is high.
In addition, these films, sheet material are generally used in the living space most at one's side of family, and the hand directly with people connects
Tactile situation is also a lot, also requires for the top coat materials endowing antibacterial such as these films, sheet material.
In addition, the applicant etc. propose in the past cause with oligomer of the alkoxysilyl containing fluoro-alkyl and
Microcosmic salt plasma liquid with alkoxysilyl the hydrolysis of alkoxysilyl is carried out in alcoholic solution and
Obtained various Nano composite granules (referring for example to patent document 3~5).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2009-216750 publications
Patent document 2：Japanese Unexamined Patent Publication 2011-74105 publications
Patent document 3：Japanese Unexamined Patent Publication 2007-270124 publications
Patent document 4：Japanese Unexamined Patent Publication 2009-209349 publications
Patent document 5：Japanese Unexamined Patent Publication 2010-77383 publications
The content of the invention
Problems to be solved by the invention
But so that foregoing Nano composite granules contain in the case of resin, it is difficult to obtain the excellent resin of the transparency
Composition.
Therefore, it is a first object of the present invention to provide the transparency, adaptation and the excellent polyester resin composition of soil resistance
Thing.In addition, it is a second object of the invention to provide the transparency, adaptation, soil resistance, antibiotic property and antiviral property are excellent
Polyester and resin composition.
The solution used to solve the problem
The present inventor etc. carry out further investigation result and found in view of the above problems, are containing polyester resin (A), (methyl) third
Olefin(e) acid based polymer (B), the monomer (C) with (methyl) acryloyl group, the polyester of organo-metallic compound (D) and solvent (E)
Contain at least one in the oligomer and its hydrolysate containing fluoro-alkyl shown in following formulas (1) in resin combination
When planting fluorochemical (F), there is excellent soil resistance in the state of the transparent and adaptation for remaining excellent, further contain
When having selected from least one of the salt and the hydrolysate of the salt shown in following formulas (2) compound (G), maintain excellent
The transparency, adaptation and there is excellent antibiotic property and antiviral property while soil resistance, so as to complete the present invention.
That is, (1) of the invention provides a kind of polyester and resin composition, it is characterised in that it contains polyester resin (A), (first
Base) acrylic acid series polymeric compounds (B), the monomer (C) with (methyl) acryloyl group, organo-metallic compound (D), solvent (E) and
Selected from least one of oligomer and its hydrolysate containing fluoro-alkyl fluorochemical (F) shown in following formulas (1).
(in formula, R1And R2Expression-(CF2)p- Y bases or-CF (CF3)-[OCF2CF(CF3)]q-OC3F7Base, R1And R2Optionally
For identical group or different groups, R1And R2In Y represent hydrogen atom, fluorine atom or chlorine atom, p and the integer that q is 0~10.
R3、R4And R5Optionally identical group or different groups, R3、R4And R5Represent the straight-chain of carbon number 1~5 or the alkyl of branched.m
For 2~3 integer.)
Further contain in the salt and its hydrolysate shown in following formulas (2) in addition, (2) of the invention are provided
The polyester and resin composition of foregoing (1) of at least one compound (G).
(in formula, A represents phosphorus atoms or nitrogen-atoms.R6、R7And R8Represent the straight-chain of carbon number 1~18 or the alkane of branched
Base.R9Represent the straight-chain of carbon number 1~5 or the alkyl of branched.N represents 1~8 integer.X-Represent anionic group.)
The effect of invention
According to the present invention it is possible to provide the transparency, adaptation and the excellent polyester and resin composition of soil resistance.In addition, root
According to the present invention, the transparency, adaptation, soil resistance, antibiotic property and the excellent polyester and resin composition of antiviral property can be provided.
Brief description of the drawings
Fig. 1 be embodiment 1 in, handled before polyester fiber electron micrograph.
Fig. 2 be embodiment 1 in, shone with the electron microscope of the polyester fiber after polyester and resin composition sample spin coating
Piece.
Embodiment
The polyester and resin composition of the present invention, it is characterised in that it contains polyester resin (A), (methyl) acrylic acid series and gathered
Compound (B), the monomer (C) with (methyl) acryloyl group, organo-metallic compound (D), solvent (E) and selected from following formulas
(1) at least one of oligomer containing fluoro-alkyl and its hydrolysate shown in fluorochemical (F),
(in formula, R1And R2Expression-(CF2)p- Y bases or-CF (CF3)-[OCF2CF(CF3)]q-OC3F7Base, R1And R2Optionally
For identical group or different groups, R1And R2In Y represent hydrogen atom, fluorine atom or chlorine atom, p and the integer that q is 0~10.
R3、R4And R5Optionally identical group or different groups, R3、R4And R5Represent the straight-chain of carbon number 1~5 or the alkyl of branched.m
For 2~3 integer.)
It should be noted that in the present invention, referring to both " acrylate " and " methacrylate " or any one
" (methyl) acrylate " is recited as in the case of person, is referred to " acrylic acid " and " methacrylic acid " both or any one
In the case of be recited as " (methyl) acrylic acid ", refer to " acryloyl group " and " methylacryloyl " both or any one
In the case of be recited as " (methyl) acryloyl group ".
The polyester resin (A) of the polyester and resin composition of the present invention is by including the compound with ester formative functional group
The polymerisation of reactive feedstock manufacture.Ester formative functional group refers to that ester can be formed with carboxyl or hydroxyl reaction
The functional group of key.Ester formative functional group includes the ester formative of carboxyl, hydroxyl, the ester formative deriveding group of carboxyl and hydroxyl
Deriveding group.The ester formative deriveding group of carboxyl refer to carboxyl carry out acid anhydrides, chloride, halogenation and it is derivative obtain,
The group of ester bond is formed with hydroxyl reaction.The ester formative deriveding group of hydroxyl refers to that hydroxyl carries out acid esterification etc. and spread out
It is raw to obtain, with other carboxyl reactions and form the group of ester bond.Particularly ester formative functional group is carboxyl or hydroxyl, from poly-
From the viewpoint of reactivity during the manufacture of ester resin is good preferably.
Reactive feedstock is for example containing polybasic carboxylic acid composition and glycol component.
Polybasic carboxylic acid composition is replaced into by carboxylic for the carboxyl in the polybasic carboxylic acid and polybasic carboxylic acid more than binary
It is more than one or both of group of ester formative derivative composition of ester formative deriveding group derived from base.
As polybasic carboxylic acid composition, such as aromatic dicarboxylic acid, aliphatic dicarboxylic acid can be included.It is used as aromatic series dicarboxyl
Acid, can include for example terephthalic acid (TPA), M-phthalic acid, phthalic acid, diphenic acid, naphthalenedicarboxylic acid, 1,2- naphthalene dicarboxylic acids,
Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 1,5- naphthalene dicarboxylic acids, 2,6- naphthalene dicarboxylic acids etc., in addition, as aliphatic dicarboxylic acid, can include for example straight
Chain, the oxalic acid of side chain or ester ring type, malonic acid, butanedioic acid, maleic acid, itaconic acid, glutaric acid, adipic acid, pimelic acid, 2,2- bis-
Methylglutaric acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid, 1,3- cyclopentane dicarboxylic acids, 1,4- cyclohexane dicarboxylic acids,
Diglycollic acid, thio-2 acid etc..
In addition, as polybasic carboxylic acid composition, the dicarboxylic acids with metal sulfamate alkali, tricarboxylic anhydride, quaternary can be included
More than the ternarys such as acid anhydrides polybasic carboxylic acid and their ester formative derivative etc..It is used as the dicarboxyl with metal sulfamate alkali
Acid and its ester formative derivative (dicarboxylic acids hereinafter collectively referred to as with metal sulfamate alkali), can be included between such as 5- sulfo groups
Phthalic acid, 2- sulfoisophthalic acids, 4- sulfoisophthalic acids, sulfoterephthalic, 4- sulfo group naphthalene -2,6- dicarboxylic acids
Deng alkali metal salt and their ester formative derivative.In addition, spreading out as polybasic carboxylic acid more than ternary and its ester formative
Biology, can include for example benzene-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid, mellophanic acid, Pyromellitic Acid, benzene pentacarbonic acid,
Mellitic acid, cyclopropane -1,2,3- tricarboxylic acids, pentamethylene -1,2,3,4- tetrabasic carboxylic acids, ethane tetrabasic carboxylic acid and their ester formative
Derivative etc..
Polybasic carboxylic acid composition is used alone a kind of or combines two or more use.In these polybasic carboxylic acid compositions, to benzene
The aromatic dicarboxylic acids such as dioctyl phthalate, M-phthalic acid, 2,6 naphthalene dicarboxylic acid, butanedioic acid, adipic acid, decanedioic acid, dodecanedioic acid
Deng aliphatic dicarboxylic acid because the easiness of reaction, resulting cementability, weatherability, the durability of resin etc. are excellent and excellent
Choosing.Particularly preferably as polybasic carboxylic acid composition, using only aromatic dicarboxylic acid or aromatic dicarboxylic acid be polybasic carboxylic acid into
The main component divided.
As glycol component, such as ethylene glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, five ethylene glycol, six can be included
The polyethylene glycol such as ethylene glycol, seven ethylene glycol, eight ethylene glycol, propane diols, dipropylene glycol, tripropylene glycol, four propane diols etc. are poly-
Propane diols, 1,3-PD, 1,3-BDO, BDO, 1,5-PD, 1,6- hexylene glycols, 2,2- dimethyl -1,3-
Propane diols, 2- ethyl -2- butyl -1,3- propane diols, 2- ethyl -2- isobutyl group -1,3- propane diols, 2,2,4- trimethyls -1,6-
Hexylene glycol, 1,2- cyclohexanedimethanols, 1,3- cyclohexanedimethanols, 1,4 cyclohexane dimethanol, 2,2,4,4- tetramethyls -1,3-
Cyclobutanediol, 4,4 '-dihydroxybiphenyl phenol, 4,4 '-methylene biphenol, 4,4 '-isopropylidenediphenol, 1,5- dihydroxy
Naphthalene, 2,5- dihydroxy naphthlenes, 2,2- double (4- hydroxy phenyls) propane (bisphenol-A), bisphenol Ss etc..Glycol component is used alone a kind of
Or combine two or more use.Especially as glycol component, the butanediol such as ethylene glycol, diethylene glycol (DEG), BDO, 1,
The acid esterification of the dihydric alcohols such as the hexylene glycols such as 6- hexylene glycols, 1,4 cyclohexane dimethanol, neopentyl glycol, bisphenol-A, their hydroxyl
Thing is excellent and preferred due to easiness, the resulting durability of resin of reaction etc..
The dicarboxylic acid component contained in reaction raw materials and the amount of glycol component, are preferably adjusted to relative to dicarboxylic acid component
The ratio between total moles of glycol component of total mole number be in the range of 1~2.5.
In addition, as reaction raw materials, from the viewpoint of adaptation and reactivity is improved, being preferably imported with hydroxyl in molecule
The compound of base, as this compound, can be included such as pentaerythrite, trimethylolpropane, dimethylolpropionic acid.
Ester formative derivative containing polybasic carboxylic acid, the feelings containing dihydric alcohol in glycol component in polybasic carboxylic acid composition
Under condition, polyester resin (A) can pass through as polybasic carboxylic acid ester formative derivative and dihydric alcohol ester exchange reaction the
The second segment that one section of reaction and the reaction product obtained using first paragraph reaction carry out polycondensation reacts to manufacture.First paragraph is anti-
In Ying Zhong, reaction system can from initially containing total overall reaction raw material, a part can also be added in ester polycondensation reaction in addition
It is added to reaction system., will reaction under the non-active gas atmosphere such as in nitrogen, under condition of normal pressure in the case of disposably feeding intake
Slowly heating is heated to 150~260 DEG C to system, thus carries out ester exchange reaction.Second segment is reacted for example at 6.7hPa (5mmHg)
Carried out under following decompression, within the temperature range of 160~280 DEG C.In first paragraph reaction and second segment reaction, when any
Phase, known titanium, antimony, lead, zinc, magnesium, calcium, manganese, alkali metal compound etc. can be added into reaction system as catalysis
Agent.
The content of polyester resin (A) in the polyester and resin composition of the present invention is suitably selected, it is preferred that being 10~99
Quality %, particularly preferably 25~90 mass %.More preferably 30~80 mass %.
(methyl) acrylic acid series polymeric compounds (B) of the polyester and resin composition of the present invention is so that good with the adaptation of base material
Good composition, obtained from make it that the polymer raw for only including the polymerization monomer with (methyl) acrylic acid series structure polymerize
Polymer causes the polymer raw using the polymerization monomer with (methyl) acrylic acid series structure as main component to polymerize
Obtained from polymer.There is (methyl) acrylic acid series as the polymer raw as (methyl) acrylic acid series polymeric compounds (B)
The monomer of structure, can include such as acrylic acid, methacrylic acid, (methyl) acrylate, (methyl) acrylamide monomer
Deng, more specifically, can include (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate,
(methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl
Ester, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, ethylene glycol two (methyl) third
Olefin(e) acid ester, ethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, hexylene glycol two (methyl) acrylate etc.
(methyl) acrylate；(methyl) alkyl acrylates such as (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate
Epoxide Arrcostab；(methyl) acrylic acid 2- hydroxy methyls, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxyls third
Ester etc. (methyl) hydroxyalkyl acrylates；(methyl) acrylic acid N, N dimethyl amino ethyl ester, (methyl) acrylic acid N, N diethyl
Base amino ethyl ester, (methyl) acrylic acid N, N dimethyl amino propyl ester, (methyl) acrylic acid N, N diethylamino propyl ester etc. are nitrogenous
(methyl) acrylate；N, N dimethyl amino-ethyl (methyl) acrylamide, N, N diethylaminos ethyl (methyl) propylene
Acid amides, N, N dimethyl aminopropyl (methyl) acrylamide, N, N diethyl amino propyls (methyl) acrylamide, N isopropyls
(methyl) acrylamide etc. (methyl) acrylamide monomer；(methyl) glycidyl acrylate etc..
(methyl) acrylic acid series polymeric compounds (B) can be (methyl) acrylate, (methyl) acrylamide, more specifically
(methyl) alkoxyalkyl acrylate, (methyl) hydroxyalkyl acrylates, nitrogenous (methyl) acrylate, (methyl) third
Acrylamide, (methyl) glycidyl acrylate etc. have only a kind of in the polymerization monomer of (methyl) acrylic acid series structure
Polymer, the copolymer of the two or more polymerization monomer with (methyl) acrylic acid series structure, or it is one or two kinds of with
On polymerization monomer with (methyl) acrylic acid series structure and ethylenically unsaturated monomer copolymer.
It polymerize the ethylenically unsaturated monomer used in the copolymerization with monomer as with (methyl) acrylic acid series structure,
The olefinic with functional group such as the ethylenically unsaturated monomer containing carboxylic acid such as itaconic acid, (methyl) acrylonitrile can be included unsaturated
Monomer, vinyl acetate, propionate, styrene, α-methylstyrene, allyl amine, Ethylenimine etc..
(methyl) acrylic acid series polymeric compounds (B) can be one or more kinds of combinations.
As (methyl) acrylic acid series polymeric compounds (B), the part or complete as the monomer of polymer raw is preferably such that
Portion's polymer obtained from the polymer raw polymerization of nitrogenous monomer.It is used as nitrogenous (methyl) acrylic acid series polymeric compounds (B)
Monomer, can include (methyl) acrylic acid N, N dimethyl amino ethyl ester, (methyl) acrylic acid N, N diethylamino ethyl ester,
(methyl) acrylic acid N, nitrogenous (methyl) propylene such as N dimethyl amino propyl ester, (methyl) acrylic acid N, N diethylamino propyl ester
Acid esters, N, N dimethyl amino-ethyl (methyl) acrylamide, N, N diethylaminos ethyl (methyl) acrylamide, N, N diformazans
Base aminopropyl (methyl) acrylamide, N, N diethyl amino propyls (methyl) acrylamide, N isopropyls (methyl) acryloyl
Amine etc. (methyl) acrylamide, allyl amine, Ethylenimine.It is preferably (methyl) acrylic acid N, N dimethyl amino among them
Ethyl ester, (methyl) acrylic acid N, N diethylamino ethyl ester, (methyl) acrylic acid N, N dimethyl amino propyl ester, (methyl) acrylic acid
N, N diethylamino propyl ester, N isopropyls (methyl) acrylamide.
It is not particularly limited for the consumption of the monomer of nitrogenous (methyl) acrylic acid series polymeric compounds (B), according to relative
In nitrogenous (methyl) acrylic acid series polymeric compounds (B) of the total amount of the polymer raw of (methyl) acrylic acid series polymeric compounds (B)
The quality ratio meter of monomer is 0.5~100 mass %, be preferably 1~60 mass %.
For the polymerization for polymerizeing, obtaining (methyl) acrylic acid series polymeric compounds (B) as the monomer of polymer raw is not had
It is particularly limited to, suitably using method known to polymerisation in solution, suspension polymerisation, emulsion polymerization etc..Organic solvent will be used
The situation of polymerisation in solution as an example, be carried out as follows and illustrate, be used as the polymer solvent of (methyl) acrylic acid series polymeric compounds, energy
Appropriate organic solvent is enough used, the alcohols such as methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol can be included；
Cellosolve acetate, methyl cellosolve, ethyl cellosolve, normal-butyl cellosolve, ethylene glycol monoisobutyl ether, n-propyl cellosolve etc. are molten
Fine agent class；Propylene glycol n-butyl ether, methyl proxitol, propane diols phenyl ether, dipropylene glycol methyl ether, propylene glycol methyl
The propane diols ethers such as ether acetic acid ester；Toluene, ethyl acetate, butyl acetate, acetone, MEK, fragrant family (petroleum distillate) are molten
Agent, phthalic acid ester system plasticizer, alkyl phosphate etc., if but (methyl) acrylic acid series polymeric compounds can dissolve or point
Scattered solvent is then not limited to these solvents.As polymer solvent if the easiness in view of reaction, preferably methanol, ethanol,
Normal propyl alcohol, isopropanol, acetone, MEK, toluene, ethyl acetate.
The content of (methyl) acrylic acid series polymeric compounds (B) in the polyester and resin composition of the present invention is suitably selected, a lot
In the case of, it is preferably 0.1~250 mass parts, particularly preferably 0.5~200 mass relative to the mass parts of polyester resin (A) 100
Part, more preferably 1~150 mass parts.
The present invention polyester and resin composition the monomer (C) with (methyl) acryloyl group, for by with (methyl) third
The synergy of olefin(e) acid based polymer (B) and further improve the cementability with base material and the composition of adaptation.With (methyl)
The monomer that the monomer (C) of acryloyl group is polymerize for the irradiation by heating or active energy beam.And being used as has (first
Base) acryloyl group monomer (C), the preferably monomer of active energy ray-curable.As with (methyl) acryloyl group
The active energy ray-curable monomer with (methyl) acryloyl group of monomer (C), can include and for example cause ethylene glycol, one
The alcohol such as contracting DPG, polyethylene glycol, propane diols, dipropylene glycol, tripropylene glycol, trimethylolpropane, pentaerythrite with
(methyl) acrylic acid carries out the monomer of esterification；So that phthalic acid, maleic acid, isocyanuric acid etc. carry out ester with allyl alcohol
The monomer changed；So that phthalic acid, maleic acid, isocyanuric acid etc. are esterified with (methyl) glycidyl acrylate
Monomer etc..Monomer (C) with (methyl) acryloyl group can be one or more kinds of combinations.
The content of the monomer (C) with (methyl) acryloyl group in the polyester and resin composition of the present invention is suitably selected,
But relative to the mass parts of polyester resin (A) 100, be preferably 0.1~40 mass parts, particularly preferably 0.5~30 mass parts, enter
One step is preferably 1~20 mass parts.
The organo-metallic compound (D) of the polyester and resin composition of the present invention is raising polyester and resin composition of the invention
In polyester resin (A) and (methyl) acrylic resin (B) compatibility composition.Therefore the polyester resin of the present invention is passed through
Composition contains organo-metallic compound (D), can the present invention polyester and resin composition in dispersed polyester resin (A)
(methyl) acrylic acid series polymeric compounds (B).
As organo-metallic compound (D), metal alkoxide, metal acrylate, metallo-chelate etc. can be included, is preferably had
There are the metallic atoms such as zirconium, titanium, aluminium, silicon.As organo-metallic compound (D), such as four zirconium-n-propylates, four n-butanols can be included
Double (ethyl acetone acid) zirconiums of zirconium, four acetylacetone,2,4-pentanedione zirconiums, three butoxy single acetyl acetone zirconiums, only son's epoxide acetylacetone,2,4-pentanedione, two fourth oxygen
Double (ethyl acetone acid) zirconiums of base, three butoxy monostearate zirconiums, titanium tetraisopropylate, four n-butyl titaniums, butanol titanium dimer, four-
It is double (ethohexadiol) titaniums of double (acetylacetone,2,4-pentanedione) titaniums of 2-Ethylhexyl Alcohol titanium, diisopropoxy, four titanium acetylacetones, two octyloxies, two different
Propoxyl group double (oacetic acid) titanium, aluminium acetylacetonate, monomethyl triisocyanate silane, tetraisocyanate silane, tetramethyls
TMOS, tetraethoxysilane, MTMS, MTES, the isopropoxy silane of methyl three, third
Base trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3,3,3- trifluoro propyls trimethoxy silane,
Dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane,
Aminomethyl phenyl dimethoxysilane etc..Organo-metallic compound (D) can be one or more kinds of combinations.
The content of organo-metallic compound (D) in the polyester and resin composition of the present invention is suitably selected, but relative to
The mass parts of polyester resin (A) 100 are preferably 1~60 mass parts, particularly preferably 3~50 mass parts, more preferably 5~40
Mass parts.
The solvent (E) of the polyester and resin composition of the present invention is if can be with dissolved polyester resin (A) and (methyl) acrylic acid series
Polymer (B) and can dissolve or dispersed other compositions are then not particularly limited, can include for example methanol, ethanol,
The alcohols such as normal propyl alcohol, isopropanol, n-butanol, isobutanol；Cellosolve acetate, methyl cellosolve, ethyl cellosolve, normal-butyl are molten
The dioxanes such as fine agent, ethylene glycol monoisobutyl ether, n-propyl cellosolve；Propylene glycol n-butyl ether, methyl proxitol, propylene glycol phenyl
The propane diols ethers such as base ether, dipropylene glycol methyl ether, methyl proxitol acetate；Toluene, ethyl acetate, acetic acid fourth
Ester, acetone, MEK, fragrant family (petroleum distillate) solvent, phthalic acid ester system plasticizer, alkyl phosphate etc., they
Can be one or more kinds of combinations.In addition, solvent (E) can be in the manufacture of (methyl) acrylic acid series polymeric compounds (B)
The reaction dissolvent used.That is, solvent (E) can be used as the manufacture of (methyl) acrylic acid series polymeric compounds (B)
Reaction dissolvent, to resulting reaction solution, i.e., to solvent (E) dissolve (methyl) acrylic acid series polymeric compounds (B) solution
The middle other compositions of mixing, manufacture the polyester and resin composition of the present invention.
The content of solvent (E) in the polyester and resin composition of the present invention is suitably selected, preferably 10~99 mass %, spy
You Xuanwei not 20~95 mass %.
The oligomer containing fluoro-alkyl shown in the formula (1) of the polyester and resin composition of the present invention and its hydrolysis production
At least one of thing fluorochemical (F), is, for polyester and resin composition, to maintain the same of excellent transparent and cementability
When assign the composition of excellent soil resistance.
The oligomer containing fluoro-alkyl of the polyester and resin composition of the present invention is represented by following formulas (1).
(in formula, R1And R2Expression-(CF2)p- Y bases or-CF (CF3)-[OCF2CF(CF3)]q-OC3F7Base, R1And R2Optionally
For identical group or different groups, R1And R2In Y represent hydrogen atom, fluorine atom or chlorine atom, p and the integer that q is 0~10.
R3、R4And R5Optionally identical group or different groups, R3、R4And R5Represent the straight-chain of carbon number 1~5 or the alkyl of branched.m
For 2~3 integer.)
It is used as the R in formula (1)3、R4And R5The straight-chain or the alkyl of branched of shown carbon number 1~5, can be included
Methyl, ethyl, propyl group, butyl, amyl group etc..
Three alcoxyl such as by causing trimethoxyvinyl silane of the oligomer containing fluoro-alkyl shown in formula (1)
Base vinyl silanes react to manufacture (referring for example to Japanese Unexamined Patent Publication 2002-338691 publications, day with peroxidating fluoro alkanoyl
This JP 2010-77383 publications).
The hydrolysate of the oligomer containing fluoro-alkyl shown in the formula (1) of the polyester and resin composition of the present invention is logical
The product generated containing the hydrolyzing oligomer of fluoro-alkyl shown in formula (1) is crossed, contains fluoro-alkyl as shown in formula (1)
Oligomer method for hydrolysis, be not particularly limited, can be the method for the catalyst using alkali, acid, or without catalyst
The method of progress.As the base catalyst used in hydrolysis, such as ammoniacal liquor, sodium hydroxide, potassium hydroxide, bicarbonate can be included
The alkali such as sodium, sodium carbonate, potassium carbonate.In addition, as the acid catalyst used in hydrolysis, the acid such as hydrochloric acid, acetic acid can be included.
The polyester and resin composition of the present invention contains the hydrolysate of the oligomer containing fluoro-alkyl shown in formula (1)
In the case of, the oligomer containing fluoro-alkyl shown in formula (1) can be hydrolyzed or other to exist with only existing its state
The state hydrolysis of composition.Specifically, it can include for example：(i) manufacture first only shown in formula (1) containing the low of fluoro-alkyl
Polymers is dissolved in solvent (E) solution, and the oligomer containing fluoro-alkyl shown in formula (1) is then carried out in the solution
Hydrolysis, then resulting hydrating solution and other compositions are mixed and polyester and resin composition is manufactured；(ii) manufacture first
Oligomer containing fluoro-alkyl and polyester resin (A) shown in formula (1) are all dissolved in solvent (E) solution, then exist
The hydrolysis of the oligomer containing fluoro-alkyl shown in formula (1) is carried out in the solution, then by resulting hydrating solution and its
Its composition mixes and manufactures polyester and resin composition etc..Among them, preferably as above-mentioned method (ii), there is polyester tree
The hydrolysis of the oligomer containing fluoro-alkyl in the solution of fat (A), shown in progress formula (1).
Oligomer containing fluoro-alkyl shown in the formula (1) and its hydrolysis in the polyester and resin composition of the present invention
The content of at least one of product fluorochemical (F) is suitably selected, it is preferred that for 0.1~10 mass %, particularly preferably
For 0.5~5 mass %.It should be noted that the polyester and resin composition of the present invention contains contains fluoro-alkyl shown in formula (1)
Oligomer and both its hydrolysates in the case of, above-mentioned content is both total content.In addition, shown in formula (1)
The content of the hydrolysate of oligomer containing fluoro-alkyl, be for hydrolysis before formula (1) shown in containing the oligomeric of fluoro-alkyl
The content of the oligomer containing fluoro-alkyl shown in formula (1) before hydrolysis during thing.That is, containing shown in formula (1)
The content of the hydrolysate of the oligomer of fluoro-alkyl be scaled hydrolysis before formula (1) shown in containing the oligomeric of fluoro-alkyl
The scaled value of thing.
The polyester and resin composition of the present invention can also contain in the salt and its hydrolysate shown in formula (2)
At least one compound (G).And by the polyester and resin composition of the present invention also contain salt shown in the formula (2) and its
At least one of hydrolysate compound (G), while the excellent transparency of maintenance, cementability and soil resistance, with excellent
Antibiotic property and antiviral property.
The salt shown in the formula (2) of the polyester and resin composition of the present invention and its compound in hydrolysate
(G) it is, for polyester and resin composition, excellent antibacterial to be assigned while the excellent transparency of maintenance, cementability and soil resistance
The composition of property and antiviral property.
There is the bacterium of antibacterial effect as the polyester and resin composition by the present invention, such as large intestine bar can be included
Bacterium, hay bacillus, staphylococcus aureus, Pseudomonas aeruginosa etc..In addition, having as the polyester and resin composition by the present invention
There is the virus of antiviral effect, influenza A virus (people, bird, pig), influenza B virus, parainfluenza virus, first can be included
Hepatitis viruse, measles virus, herpesviral, mumps virus, hydrophobin of~penta type etc. have tunicary virus, and promise is such as
The non-enveloped virus such as virus.
Shown in for example following formulas (2) of salt of the polyester and resin composition of the present invention.
(in formula, A represents phosphorus atoms or nitrogen-atoms.R6、R7And R8Represent the straight-chain of carbon number 1~18 or the alkane of branched
Base.R9Represent the straight-chain of carbon number 1~5 or the alkyl of branched.N represents 1~8 integer.X-Represent anionic group.)
R in formula (2)6、R7And R8The alkyl of straight-chain or branched for carbon number 1~18, specifically, can be enumerated
Go out methyl, ethyl, propyl group, butyl, amyl group, octyl group, dodecyl, octadecyl etc..R6、R7And R8It can be each identical base
Group or different groups.In addition, the R in formula (2)9The alkyl of straight-chain or branched for carbon number 1~5, specifically, can be arranged
Methyl, ethyl, propyl group, butyl, amyl group are enumerated, wherein, particularly preferably methyl.In addition, n in formula (2) for 1~8 it is whole
Number, preferably 3.In addition, the X in formula (2)-Represent anionic group.It is used as X-Anionic group, benzo three can be included
Oxazolinium ion, fluorine ion, chlorion, bromide ion, iodide ion, BF4 -、PF6 -、N(SO2CF3)2 -、PO2(OMe)3 -、PS2(OEt)2 -、
(CO2Me)2PhSO3 -Deng anionic group, wherein, preferably chlorion.
The salt shown in the formula (2) of the polyester and resin composition of the present invention and its compound in hydrolysate
(G), compared with ammonium salt, from the viewpoint of antiviral activity is further improved, preferably microcosmic salt.
The hydrolysate of salt shown in the formula (2) of the polyester and resin composition of the present invention is by formula (2) Suo Shi
Salt hydrolysis and the product that generates, as the method for hydrolysis of the salt shown in formula (2), be not particularly limited, can be to make
With the method for alkali, the catalyst of acid, or the method carried out without catalyst.As the base catalyst used in hydrolysis, it can arrange
Enumerate the alkali such as ammoniacal liquor, sodium hydroxide, potassium hydroxide, sodium acid carbonate, sodium carbonate, potassium carbonate.It is used as the acid used in hydrolysis
Catalyst, can include the acid such as hydrochloric acid, acetic acid.
In the case that the polyester and resin composition of the present invention contains the hydrolysate of the salt shown in formula (2), formula (2)
Shown salt can be hydrolyzed with only existing its state or there is the hydrolysis of the state of other compositions.Specifically, it can arrange
Enumerate for example：(iii) solution that the salt only shown in formula (2) is dissolved in solvent (E) is manufactured first, then in the solution
The middle hydrolysis for carrying out the salt shown in formula (2), resulting hydrating solution and other compositions are then mixed and manufacture polyester
Resin combination；(iv) salt first shown in manufacture formula (2), contains fluoro-alkyl shown in polyester resin (A) and formula (1)
Oligomer be all dissolved in solvent (E) solution, then carried out in the solution shown in formula (1) containing fluoro-alkyl
The hydrolysis of the salt shown in formula (2) is carried out while the hydrolysis of oligomer, then by resulting hydrating solution and it is other into
Divide mixing and manufacture polyester and resin composition etc..Among them, preferably as above-mentioned method (iv), there is polyester resin
(A) hydrolysis of the salt shown in formula (2) is carried out in the solution of the oligomer containing fluoro-alkyl and shown in formula (1).
At least one in the salt and its hydrolysate shown in formula (2) in the polyester and resin composition of the present invention
The content for planting compound (G) is suitably selected, it is preferred that being 0.1~50 mass %, particularly preferably 0.5~30 mass %.Need
It is noted that the polyester and resin composition of the present invention contains the feelings of salt and both its hydrolysates shown in formula (2)
Under condition, above-mentioned content is both total contents.In addition, the content of the hydrolysate of salt shown in formula (2), is for before hydrolysis
Formula (2) shown in salt when hydrolysis before formula (2) shown in salt content.That is, shown in formula (2)
The content of the hydrolysate of salt is the scaled value for the content for being scaled the salt shown in the formula (2) before hydrolysis.
Manufacture method for the polyester and resin composition of the present invention is not particularly limited, in solvent (E) mixed polyester tree
Fat (A), (methyl) acrylic acid series polymeric compounds (B), the monomer (C) with (methyl) acryloyl group, organo-metallic compound (D),
Order, the method for fluorochemical (F) and compound (G) are suitably selected.
Consider from the stability-enhanced viewpoint of polyester and resin composition, polyester and resin composition of the invention preferably will
Containing polyester resin (A), the A liquid of solvent (E) and fluorochemical (F) or contain polyester resin (A), solvent (E), fluorine-containing
The A liquid of compound (F) and compound (G) is with containing (methyl) acrylic acid series polymeric compounds (B), the list with (methyl) acryloyl group
What the B liquid of body (C), organo-metallic compound (D) and solvent (E) was obtained by mixing.
From the viewpoint of the workability of A liquid is excellent, polyester resin (A), fluoropolymer (F) and root preferably in A liquid
It is 40~100 mass %, preferably 60~100 mass % according to the total content (A+F+G) for the compound (G) for needing to mix.In addition, from
From the viewpoint of the workability of B liquid is excellent, (methyl) acrylic acid series polymeric compounds (B) preferably in B liquid, with (methyl) acryloyl
The monomer (C) of base and the total content (B+C+D) of organo-metallic compound (D) are 2~40 mass %, preferably 5~20 mass %.
As A liquid, preferably containing shown in polyester resin (A), solvent (E) and formula (1) containing the oligomeric of fluoro-alkyl
In the liquid of thing, the hydrolyzing oligomer containing fluoro-alkyl shown in formula (1) is obtained.In addition, as A liquid, preferably containing
There is the liquid of polyester resin (A), solvent (E), the oligomer containing fluoro-alkyl shown in formula (1) and the salt shown in formula (2)
In body, the salt hydrolysis shown in formula (1) shown in oligomer and formula (2) containing fluoro-alkyl are obtained.
Relative to the combined amount of the B liquid of A liquid, (B liquid/A liquid) is calculated as 0.1~2.5, preferably 1.0~2.0 in mass ratio.
The salt shown in oligomer containing fluoro-alkyl and formula (2) shown in formula (1) has tri-alkoxy monosilane
Base is used as the position that can be hydrolyzed.Therefore, it is fluorine-containing by by the hydrolyzing oligomer containing fluoro-alkyl shown in aforementioned formula (1)
Connected between the reaction residue of the oligomer of substituted alkyl by siloxanes key and form three-dimensional network, on the other hand, containing fluoroalkane
Reaction residue and polyester resin (A) the formation chemical bond or intermolecular hydrogen bonding of the oligomer of base, the oligomer containing fluoro-alkyl
Reaction residue is immobilized in polyester resin (A).In addition, passing through the oligomer shown in formula (1) containing fluoro-alkyl and logical
The hydrolysis of salt shown in formula (2) is carried out simultaneously in the same solution, the reaction residue and salt of the oligomer containing fluoro-alkyl
Reaction residue connected by siloxanes key and form three-dimensional network, on the other hand, the reaction of the oligomer containing fluoro-alkyl is residual
Reaction residue and polyester resin (A) the formation chemical bond or intermolecular hydrogen bonding of base and salt, the oligomer containing fluoro-alkyl it is anti-
The reaction residue of residue and salt is answered to be immobilized in polyester resin (A).So as to which the polyester and resin composition of the present invention contains
Immobilization has the polyester resin (A) of the reaction residue of the oligomer containing fluoro-alkyl or the oligomer containing fluoro-alkyl and salt
In the case of, the solidfied material formed using this polyester and resin composition, soil resistance can be caused and assign as needed it is anti-
Bacterium property, antiviral property continue for a long time.Particularly polyester and resin composition of the invention, which contains immobilization, has containing the low of fluoro-alkyl
In the case of the polyester resin (A) of the reaction residue of polymers and salt, pass through the reaction residue of the oligomer containing fluoro-alkyl
Effect so that the reaction residue of salt is more optionally present in the surface of solidfied material, thus can effectively show antibacterial,
Antivirus action.
As the specific method in oligomer of polyester resin (A) immobilization containing fluoro-alkyl or the reaction residue of salt,
The oligomer containing fluoro-alkyl shown in mixing formula (1) in the liquid containing polyester resin (A) and solvent (E) can be included
Or the salt shown in the oligomer containing fluoro-alkyl and formula (2) shown in formula (1), then according to needing to add ammoniacal liquor,
The method for carrying out the hydrolysis of trialkoxysilyl, resulting hydrolyzate and other compositions are mixed, this hair can be manufactured
Bright polyester and resin composition.Now, the addition of ammoniacal liquor is according to addition gauge when being converted with 25 mass % ammoniacal liquor, relatively
In the oligomer containing fluoro-alkyl and salt total 1g be 1~30ml, preferably 5~15ml.In addition, reaction when being hydrolyzed
Temperature is -5~50 DEG C, preferably 0~30 DEG C, and the reaction time is 0.1~5 hour.
The polyester and resin composition of the present invention can contain increasing in the range of it will not damage effect of the present invention as needed
Quick dose, Photoepolymerizationinitiater initiater, levelling agent, wax, defoamer, releasing agent, the additive such as anti-wear agent.
As the application method of the polyester and resin composition of the present invention, pass through method of impregnation, curtain coating method, intaglio plate coating first
Method, wire rod method, spraying process, reverse roll coating method, die coating methods etc., in the polyester resin group of the surface coating present invention of base material
Compound, is then dried, removes solvent (E), and the film for including nonvolatile component is formed on the surface of base material.Then by institute's film forming
Film heating or while irradiate active energy beam for the film of institute's film forming or heat the film of institute's film forming for film
Active energy beam is irradiated, so that the film solidification of institute's film forming, the surface formation solidfied material in base material.
During with active energy beam so that the film of institute's film forming solidifies, as active energy beam, the situation of ultraviolet is used
Under, promote reaction in order to be irradiated by ultraviolet, polyester and resin composition of the invention preferably comprises Photoepolymerizationinitiater initiater.Make
For Photoepolymerizationinitiater initiater, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, 2- pi-allyls can be included
The benzoin systems such as benzoin, 2- chlorobenzene acyloins, benzophenone, to methyl benzophenone, p-dichlorobenzene ketone, p-dichlorobenzene ketone
Deng benzophenone series, diethoxy acetophenone, hydroxy acetophenone (1- hydroxy-cyclohexyl-phenyls -one, 2- hydroxy-2-methyls -1-
Phenyl-propan -1- ketone etc.), the acetophenone system such as alpha-aminoacetophenone, 2- methyl thioxanthones, ITX, 2- diurils ton
The thioxanthones such as ketone system, the azo system such as azobis isobutyronitrile, the quinone system such as anthraquinone, 2- chloroanthraquinones, phenanthrene.Various Photoepolymerizationinitiater initiaters are independent
Used using one or more combination.
In the case that the polyester and resin composition of the present invention contains Photoepolymerizationinitiater initiater, from the sensitivity of ultraviolet can be improved
From the viewpoint of property, ESCAROL 507 ethyl ester, ESCAROL 507 isopentyl ester, benzoic acid 2- are preferably comprised
The sensitizers such as dimethylamino ethyl ester, methacrylic N, N-dimethylamino ethyl ester, N methyldiethanol amine.
In the case that the polyester and resin composition of the present invention contains Photoepolymerizationinitiater initiater, the content of Photoepolymerizationinitiater initiater is appropriate
Selection, it is preferred that the mass parts of total amount 100 relative to the monomer (C) with (methyl) acryloyl group are 0.5~30 mass parts.
As active energy beam, if producing free radical corresponding to the composition of the polyester and resin composition of the present invention
Spike is then not particularly limited to induce polymerisation, as light source during irradiation ultraviolet radiation, can include such as low pressure or
High-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, xenon lamp, electrodeless discharge lamp, carbon arc lamp etc..In the case of irradiating electron beam,
Using various irradiation units, it can include such as sweep type, electron curtain type.
The solidfied material of the present invention is to be heated or irradiated active energy by the polyester and resin composition for the present invention
Measure solidfied material obtained from ray.The solidfied material of the present invention is formed at the surface of base material.
As the material of base material, it is not particularly limited, such as polyethylene terephthalate (PET) can be included, gathered
(ethylene naphthalate), polyester, paper, makrolon, acrylic resin etc..In addition, the shape for base material is not special
Limitation, can be film-form, sheet, filter shape, threadiness.In addition, base material can also be the base material of indefinite form.
The solidfied material of the present invention is obtained as follows：By method of impregnation, curtain coating method, gravure coating process, wire rod method, spraying process,
Reverse roll coating method, die coating methods etc., in the polyester and resin composition of the surface coating present invention of base material, be then dried,
Solvent (E) is removed, the film of the nonvolatile component of the polyester and resin composition comprising the present invention is formed on the surface of base material, then will
The film heating of nonvolatile component in polyester and resin composition comprising the present invention or the polyester resin composition for the present invention
Nonvolatile component irradiation active energy beam in thing, so that the nonvolatile component in the polyester and resin composition of the present invention
Solidify to obtain the solidfied material of the present invention.It should be noted that the nonvolatile component in the polyester and resin composition of the present invention refers to
Be by by the present invention polyester and resin composition dry, by the present invention polyester and resin composition in remove solvent (E) and
The composition of residual.
The polyester and resin composition of the present invention, which contains immobilization, has oligomer containing fluoro-alkyl or containing fluoro-alkyl
In the case of the polyester resin (A) of the reaction residue of oligomer and salt, the solidification formed using this polyester and resin composition
In thing, the reaction residue of the salt shown in the reaction residue and formula (2) of the oligomer containing fluoro-alkyl shown in formula (1) is such as
Corona is formed by the surface of solidfied material with the shape of radial elongation like that.Therefore, even if being fluoro-alkyl oligomer and salt
In the case of few content, the excellent transparency and adaptation are also maintained, and effectively solidfied material can be assigned excellent
Soil resistance and then excellent antibiotic property, antiviral property.
The polyester and resin composition of the present invention be applied to automobile component, electronic instrument, building materials field etc. top coat materials,
The formation of the surface finished materials of clothes, fiber etc. is used.
The structure of the present invention includes base material and is formed at the solidfied material of the invention on its surface.
The present invention is more particularly described by the following examples, but the present invention is not limited to these examples.
Embodiment
<Oligomer (F) containing fluoro-alkyl>
As the oligomer (F) (hereinafter sometimes referred to " VM ") containing fluoro-alkyl, the material of table 1 below is used.
[table 1]
<Salt (G)>
As salt, the material of table 2 below is used.
[table 2]
<The manufacture of A ' liquid>
Reaction raw materials composition according to Table 3 below, prepares the various reaction raw materials for manufacturing polyester resin.
It is then ready for possessing mixer, nitrogen inlet, thermometer, rectifying column, the capacity 1000ml for cooling down condenser
Reaction raw materials shown in Table 3 below are put into reactor by reaction vessel respectively.They are stirred in normal pressure, nitrogen atmosphere
It is warming up to while mixing after 200 DEG C, reaction temperature is to slowly warm up to 260 DEG C with 4 hours, ester exchange reaction is thus completed.
Then the solution is slowly depressurized at a temperature of 260 DEG C, holding 2 is small under conditions of 260 DEG C, 0.67hPa (0.5mmHg)
When, polycondensation reaction is thus carried out, polyester resin is obtained.
Then, 100 parts resulting of polyester resin, 270 parts of ethyl acetate are added in container, by the same of their stirrings
When at a temperature of 80~95 DEG C keep 2 hours, thus obtain the mass % of polyester resin content 27 A ' liquid.
[table 3]
1) relative to whole dicarboxylic acid components each dicarboxylic acid component mole %
2) relative to whole glycol components each glycol component mole %
<The manufacture of B liquid>
Polymer raw composition according to table 4, prepares to be used to manufacture the various of (methyl) acrylic acid series copolymer (B)
The polymer raw (polymer raw material monomer) of (methyl) acrylic acid series polymeric compounds (B).
It is then ready for the reaction appearance for possessing mixer, nitrogen inlet, thermometer, the capacity 1000ml of reflux condenser
Device, be separately added into polymer raw material monomer shown in table 4 below amount to 200 parts, 380 parts of the ethyl acetate as polymer solvent,
10 parts of toluene, 10 parts of MEK and 2 as polymerization initiator, 4 parts of 2 '-azobis isobutyronitrile gather in stream of nitrogen gas, at 80 DEG C
Close 6 hours, obtain the resin solution of (methyl) acrylic acid series polymeric compounds (B) transparent and with toughness.
There is (methyl) third shown in the resin solution addition table 4 of resulting (methyl) acrylic acid series polymeric compounds (B)
The monomer (C) (monomer (C)) and organo-metallic compound (D) of enoyl-, and then ethyl acetate is added, obtain (methyl) acrylic acid
The total content (B+C+D) of based polymer (B), the monomer (C) with (methyl) acryloyl group and organo-metallic compound (D) is 13
Quality % B liquid.
[table 4]
1) monomer of the polymer raw as (methyl) acrylic acid series polymeric compounds (B)
2) there is the monomer (C) of (methyl) acryloyl group
(embodiment 1)
Oligomer containing fluoro-alkyl is respectively added to each A ' liquid with the compounding of table 5, then added with the compounding amount of table 5
25 mass % ammoniacal liquor, carry out stirring for 5 minutes under room temperature (25 DEG C), manufacture A liquid.Then B liquid is added to the A liquid, stirs 3 points
Clock, manufactures polyester and resin composition sample.
(embodiment 2)
Without ammoniacal liquor, polyester and resin composition sample is in addition manufactured similarly to Example 1.
[table 5]
| Embodiment 1 | Embodiment 2 | |
| <A liquid> | ||
| The species of A ' liquid | a1 | a1 |
| VM addition (mg) | 20 | 20 |
| 25 mass %NH3(ml) | 0.1 | - |
| The combined amount (g) of A liquid1) | 1 | 1 |
| <B liquid> | ||
| The species of B liquid | a2 | a2 |
| The combined amount (g) of B liquid2) | 1 | 1 |
1) amount of the A liquid mixed with B liquid
2) amount of the B liquid mixed with A liquid
<Evaluation to PET film>
Polyester and resin composition sample obtained above is spun on PET film (long 1.8cm × wide 1.8cm), in room temperature
Under be dried, then at 120 DEG C heating carry out heat cure, manufacture 105 μm of thickness film sample.
The contact angle of dodecane and water, the turbidity of film sample and adaptation to the surface of the film are evaluated.Its
As a result it is as shown in table 6.In addition, will collect without processed material as blank and be recorded in table 6.
For contact angle, using the Drop Master.300 of consonance interface science, contact angle is determined.In addition, for turbid
Degree, the transmitance of light during measure 500nm will be used as reference without addition VM film sample (blank), and determine film sample
Absorbance.The value is smaller, represents more transparent.
For adaptation, according to JIS K 5600-5-6, the otch of 25 grid is formed in film sample, it is firm by thereon
Ground is pasted after adhesive tape, the release band within 5 minutes, and naked eyes confirm the stripping of film, thus carries out the evaluation of adaptation.Evaluate
Benchmark is as described below.
○：Every 25 grid remain more than 20.
×：Every 25 grid residual is less than 20.
[table 6]
| Embodiment 1 | Embodiment 2 | Blank | |
| Contact angle (°) | |||
| Dodecane | 49 | 47 | 0 |
| Water | 62 | 69 | 59 |
| Turbidity | 0.043 | 0.004 | 0 |
| Adaptation | ○ | ○ | - |
<Evaluation to PET>
The polyester and resin composition sample coating manufactured in embodiment 1 is dried in PET cloth by spin-coating method and infusion process
Afterwards, it is dried at room temperature for, then heating carries out heat cure at 120 DEG C, manufactures fiber samples.The dodecane on the surface of fiber with
The contact angle of water is determined as described above, and its result is as shown in table 7.
In addition, the electron micrograph of before processing and the fiber samples (after heat cure) handled by spin-coating method progress
Respectively as shown in Figures 1 and 2.
[table 7]
(embodiment 3~5 and comparative example 1~2)
Oligomer containing fluoro-alkyl, salt, tetraethyl-metasilicate (TEOS) are respectively added to each A ' with the compounding of table 8
Liquid, then adds 25 mass % ammoniacal liquor with the compounding of table 8, carries out stirring for 5 minutes under room temperature (25 DEG C), manufactures A liquid.Then to
The A liquid adds B liquid, stirs 3 minutes, manufactures polyester and resin composition sample.
Polyester and resin composition sample obtained above is spun on PET film (long 1.8cm × wide 1.8cm), in room temperature
Under be dried, then at 120 DEG C heating carry out heat cure, manufacture film sample.
Similarly to Example 1 to the dodecane and the contact angle of water on the surface of the film, the turbidity of film sample and close
Conjunction property is measured, and its result is as shown in table 9.In addition, will collect without processed material as blank and be recorded in table 9.
[table 8]
1) amount of the A liquid mixed with B liquid
2) amount of the B liquid mixed with A liquid
[table 9]
(antibacterial activity experiment)
As the representative of gramnegative bacterium, Escherichia coli, Escherichia coli (Escherichia coli are used
NBRC3972), as the representative of gramnegative bacterium, staphylococcus aureus, aurococcus are used
(Staphylococcus aureus subsp.aureus NBRC12732), it is thin for what is obtained in embodiment 4, embodiment 5
Film sample carries out antibiotic property experiment.
The square test film of 50mm × 50mm size is made up of film sample.Test film is encased in sterilizing culture
Ware so that Escherichia coli 2.3 × 104Individual/ml, aurococcus 2.2 × 104Individual/ml experiment bacterium solution
0.5ml is inoculated in each test film surface.
Closed the lid thereon, after being cultivated 24 hours at 25 DEG C, each test film fully washed out with broth bouillon 10ml,
At 37 DEG C after NA medium cultures 24 hours, the viable count of the culture medium is determined, is represented with clump count (cfu/ml).Its result
As shown in table 10.In addition, antibacterial tests are similarly carried out without processed material, as blank.
[table 10]
| Embodiment 4 | Embodiment 5 | Blank | |
| Staphylococcus aureus (cfu/ml) | ＜ 2.5 | ＜ 2.5 | 5.3×104 |
| Escherichia coli (cfu/ml) | ＜ 2.5 | 14 | 1.1×108 |
(evaluation on resisiting influenza virus)
The square test film of 50mm × 50mm size is made up of film sample.
Filter paper is laid in deep type culture dish, a small amount of aqua sterilisa is added.5mm or so glass system is set on filter paper
Pedestal, thereon set afore-mentioned test piece.Thereon be added dropwise in advance domestication, concentration it is also known that influenza virus substitute virus
QB bacteriophages (NBRC20012) solution 0.1ml, contacts with bacteriophage in order that obtaining material surface, covers polyethylene film
(KOYUYO、40mm×40mm).The culture dish is covered with glass plate.Same measure only prepares the measure of bacteriophage number with assembling
The number of pre-determined number, 4 hours are stood 25 DEG C of dark places.
JIS R 1706 are next based on, using host e. coli (NBRC106373), phage-infect titre, base are evaluated
In the calculating formula of the antiviral rapidoprint of the hydridization photochemical catalyst effect in the dark of following calculating formulas (1), by antiviral activity
It is used as VDEvaluated.Its result is as shown in table 11.In addition, in embodiment 4 and embodiment 5, do not add VM,
TBSP-Cl, ODTSA-Cl and 25 mass %NH3Antivirus test is similarly carried out to solidify obtained material, as sky
White 1, its result, which collects, is recorded in table 11.
It should be noted that VDValue more it is big then represent antiviral activity it is higher.
VD=log (BD/CD) (1)
VD：The dark place effect of antiviral rapidoprint
BD：The test film for not carrying out antiviral processing is stored in the phage-infect of 3 test film of the dark place after 4 hours
The average value (pfu) of titre
CD：The test film for having carried out antiviral processing is stored in the phage-infect drop of 3 test films of the dark place after 4 hours
The average value (pfu) of degree
[table 11]
| BD(pfu) | CD(pfu) | VD(pfu) | |
| Embodiment 4 | 1.7×106 | 2.6×103 | 2.8 |
| Embodiment 5 | 1.7×106 | 3.1×104 | 1.7 |
| Blank 1 | 1.7×106 | 1.7×106 | 0 |
(evaluation on anti-norovirus)
QB bacteriophages (NBRC20012) are substituted, the bacteriophages of φ 6 (NBRC105899) substituted using norovirus are substituted
Host e. coli (NBRC106373), using host Pseudomonas aeruginosa (NBRC105640), in addition with embodiment 1 and being compared
Example 1 similarly regard antiviral activity as VDEvaluated.Its result is as shown in table 12.In addition, in embodiment 4 and implementation
In example 5, VM, TBSP-Cl, ODTSA-Cl and 25 mass %NH are not added3Come solidify obtained material similarly carry out it is disease-resistant
Poison experiment, as blank 2, its result, which collects, is recorded in table 12.
[table 12]
| BD(pfu) | CD(pfu) | VD(pfu) | |
| Embodiment 4 | 1.5×106 | 3.0×101 | 4.7 |
| Embodiment 5 | 1.5×106 | 2.6×105 | 0.8 |
| Blank 2 | 1.5×106 | 1.5×106 | 0 |
(embodiment 6~7)
Oligomer containing fluoro-alkyl, salt are respectively added to each A ' liquid with the compounding of table 13, then matching somebody with somebody with table 13
Carry out stirring for 5 minutes under 25 mass % ammoniacal liquor of mixed addition, room temperature (25 DEG C), manufacture A liquid.Then B liquid, stirring 3 are added to the A liquid
Minute, manufacture polyester and resin composition sample.
[table 13]
| Embodiment 6 | Embodiment 7 | |
| <A liquid> | ||
| The species of A ' liquid | c1 | d1 |
| VM addition (mg) | 20 | 20 |
| TBSP-Cl(mg) | 10 | - |
| 0DTSA-Cl(mg) | - | 10 |
| 25 mass %NH3(ml) | 0.5 | 0.5 |
| The combined amount (g) of A liquid1) | 1 | 1 |
| <B liquid> | ||
| The species of B liquid | c2 | d2 |
| The combined amount (g) of B liquid2) | 1 | 1 |
1) amount of the A liquid mixed with B liquid
2) amount of the B liquid mixed with A liquid
Polyester and resin composition sample obtained above is spun on PET film (long 1.8cm × wide 1.8cm), in room temperature
Under be dried, then carry out heat cure at 120 DEG C, manufacture film sample.
The dodecane on surface and contact angle, turbidity and the adaptation of water of the film are surveyed similarly to Example 1
Fixed, its result is as shown in table 14.In addition, will collect without processed material as blank and be recorded in table 14.
[table 14]
| Embodiment 6 | Embodiment 7 | Blank | |
| Contact angle (°) | |||
| Dodecane | 47 | 40 | 0 |
| Water | 65 | 67 | 59 |
| Turbidity | 0.237 | 0.205 | 0 |
| Adaptation | ○ | ○ | - |
For without using comparative example during VM in embodiment 6 and 7, not implementing, but embodiment 6 and 7 is due to 12
The value of the contact angle of alkane and water is degree same as Example 1, therefore embodiment 6 and 7 also plays effect same as Example 1
Really, thus it is speculated that in the case of the VM in embodiment 6 and 7, their turbidity is deteriorated compared with embodiment 6 and 7.
(embodiment 8)
25 mass %NH are not added to A liquid3, polyester and resin composition sample is in addition manufactured similarly to Example 4.
Then, polyester and resin composition sample obtained above is spun on PET film (long 1.8cm × wide 1.8cm),
It is dried at room temperature, heating is then carried out at 120 DEG C carries out heat cure, manufactures film sample.
Similarly to Example 1 to the dodecane and the contact angle of water on the surface of the film, the turbidity of film sample and close
Conjunction property is measured, and its result is as shown in Table 15.In addition, will collect without processed material as blank and be recorded in table 15.
[table 15]
| Embodiment 8 | Blank | |
| Contact angle (°) | ||
| Dodecane | 40 | 0 |
| Water | 69 | 59 |
| Turbidity | 0.004 | 0 |
| Adaptation | ○ | - |
(anti-bacteria and anti-virus experiment)
For film sample obtained above, implement antibacterial tests and antiviral examination in the same manner as embodiment 4 and embodiment 5
Test.In addition, in order to confirm whether VM and TBSP-Cl is chemically immobilized onto in polyester, foregoing film sample is washed with ethanol,
Antibacterial tests and antivirus test are also carried out for the film sample washed.Its result is respectively as shown in table 16 and table 17.
It should be noted that carried out using the washing of ethanol by the way that film sample is impregnated in into 99% ethanol 5 minutes,
Dry 1 day at room temperature, regard dried object as the film sample after washing.
[table 16]
[table 17]
Claims (13)
1. a kind of polyester and resin composition, it is characterised in that it contains polyester resin (A), (methyl) acrylic acid series polymeric compounds
(B) monomer (C), organo-metallic compound (D), solvent (E), with (methyl) acryloyl group and selected from following formulas (1) institute
At least one of the oligomer containing fluoro-alkyl and its hydrolysate that show fluorochemical (F),
In formula, R1And R2Expression-(CF2)p- Y bases or-CF (CF3)-[OCF2CF(CF3)]q-OC3F7Base, R1And R2It is optionally identical
Group or different groups, R1And R2In Y represent hydrogen atom, fluorine atom or chlorine atom, p and the integer that q is 0~10, R3、R4And R5
Optionally identical group or different groups, R3、R4And R5The straight-chain of carbon number 1~5 or the alkyl of branched are represented, m is 2~3
Integer.
2. polyester and resin composition according to claim 1, it is characterised in that (methyl) acrylic acid series polymeric compounds
(B) it is (methyl) acrylic acid series polymeric compounds obtained from nitrogenous (methyl) acrylic acid series polymeric compounds (B) are polymerize with monomer.
3. polyester and resin composition according to claim 1 or 2, it is characterised in that described that there is (methyl) acryloyl group
Monomer (C) be the active energy ray-curable monomer with (methyl) acryloyl group.
4. according to polyester and resin composition according to any one of claims 1 to 3, it is characterised in that the organometallic
Compound (D) is selected from least one of metal alkoxide, metal acrylate and metallo-chelate.
5. according to polyester and resin composition according to any one of claims 1 to 4, it is characterised in that the fluorochemical
(F) content is 0.1~10 mass %.
6. according to polyester and resin composition according to any one of claims 1 to 5, it is characterised in that it is further containing choosing
From at least one of the salt shown in following formulas (2) and its hydrolysate compound (G),
In formula, A represents phosphorus atoms or nitrogen-atoms, R6、R7And R8Represent the straight-chain of carbon number 1~18 or the alkyl of branched, R9Table
Show the straight-chain of carbon number 1~5 or the alkyl of branched, n represents 1~8 integer, X-Represent anionic group.
7. polyester and resin composition according to claim 6, it is characterised in that the content of the compound (G) is 0.1~
50 mass %.
8. according to polyester and resin composition according to any one of claims 1 to 7, it is characterised in that it is by containing described
The A liquid of polyester resin (A), the solvent (E) and the fluorochemical (F) is with containing described (methyl) acrylic acid series polymeric compounds
(B), the B liquid of the monomer (C) with (methyl) acryloyl group, the organo-metallic compound (D) and the solvent (E) is mixed
Obtained from conjunction.
9. polyester and resin composition according to claim 8, it is characterised in that the A liquid also contains the compound
(G)。
10. polyester and resin composition according to claim 8, it is characterised in that the A liquid is containing the polyester tree
In the liquid of fat (A) and the solvent (E), obtained from the hydrolysis for carrying out the fluorochemical (F).
11. polyester and resin composition according to claim 9, it is characterised in that the A liquid is containing the polyester tree
In the liquid of fat (A) and the solvent (E), carry out the hydrolysis of the fluorochemical (F) and the compound (G) and obtain
's.
12. a kind of solidfied material, it is by being added for the polyester and resin composition any one of claim 1~11
Obtained from heat or irradiation active energy beam are solidified.
13. a kind of structure, has the solidfied material described in claim 12 on its surface.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014217092 | 2014-10-24 | ||
| JP2014-217092 | 2014-10-24 | ||
| PCT/JP2015/077274 WO2016063680A1 (en) | 2014-10-24 | 2015-09-28 | Polyester resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107074998A true CN107074998A (en) | 2017-08-18 |
Family
ID=55760725
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580057523.2A Pending CN107074998A (en) | 2014-10-24 | 2015-09-28 | Polyester and resin composition |
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| Country | Link |
|---|---|
| JP (1) | JP6067938B2 (en) |
| KR (1) | KR20170074859A (en) |
| CN (1) | CN107074998A (en) |
| WO (1) | WO2016063680A1 (en) |
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| JPWO2016178385A1 (en) * | 2015-05-01 | 2018-06-14 | 日本化学工業株式会社 | Antiviral agent, antiviral agent composition and antiviral material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0525457A (en) * | 1991-07-19 | 1993-02-02 | Nippon Oil & Fats Co Ltd | Modification of surface of polyester |
| JP3861562B2 (en) * | 2000-04-28 | 2006-12-20 | 凸版印刷株式会社 | Method for producing hard coat film |
| JP2003034761A (en) * | 2001-04-27 | 2003-02-07 | Nippon Arc Co Ltd | Hard coating composition and hard coating product |
| JP4958609B2 (en) * | 2007-04-06 | 2012-06-20 | リンテック株式会社 | Antiglare hard coat film and method for producing the same |
| JP2010235943A (en) * | 2009-03-12 | 2010-10-21 | Nippon Chem Ind Co Ltd | Nano composite powdery particle having siloxane bond as main skeleton and method for producing the same, nano composite powdery particle dispersion liquid having siloxane bond as main skeleton, and resin composition |
| JP5952654B2 (en) * | 2012-06-27 | 2016-07-13 | 株式会社ダイセル | Hard coat film and method for producing the same |
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2015
- 2015-09-28 WO PCT/JP2015/077274 patent/WO2016063680A1/en active Application Filing
- 2015-09-28 KR KR1020177008772A patent/KR20170074859A/en unknown
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| JP6067938B2 (en) | 2017-01-25 |
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