JP2018199881A - Binder for inorganic fiber and inorganic fiber mat - Google Patents
Binder for inorganic fiber and inorganic fiber mat Download PDFInfo
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- JP2018199881A JP2018199881A JP2017105629A JP2017105629A JP2018199881A JP 2018199881 A JP2018199881 A JP 2018199881A JP 2017105629 A JP2017105629 A JP 2017105629A JP 2017105629 A JP2017105629 A JP 2017105629A JP 2018199881 A JP2018199881 A JP 2018199881A
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- 239000012784 inorganic fiber Substances 0.000 title claims abstract description 134
- 239000011230 binding agent Substances 0.000 title claims abstract description 80
- 229920001577 copolymer Polymers 0.000 claims abstract description 34
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000011491 glass wool Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 239000011490 mineral wool Substances 0.000 claims description 5
- 239000012855 volatile organic compound Substances 0.000 abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005011 phenolic resin Substances 0.000 abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 42
- 238000000034 method Methods 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 8
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000011358 absorbing material Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- -1 acrylate ester Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000003232 water-soluble binding agent Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Classifications
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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
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/48—Coating with two or more coatings having different compositions
- C03C25/50—Coatings containing organic materials only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4218—Glass fibres
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Nonwoven Fabrics (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は、無機繊維用バインダー、特に、建築用の断熱材、吸音材等として好適に用いられる無機繊維マットに対して、揮発性有機化合物の放出が極めて少なく、十分な厚みを持ち、かつ優れた復元性を与える無機繊維用バインダー、及び該バインダーで処理された無機繊維マットに関する。 The present invention is a binder for inorganic fibers, in particular, an inorganic fiber mat suitably used as a heat insulating material for buildings, a sound absorbing material, etc., and emits very little volatile organic compound, has a sufficient thickness, and is excellent The present invention relates to a binder for inorganic fibers that gives high restoration properties, and an inorganic fiber mat treated with the binder.
従来、グラスウール、ロックウール等の無機繊維からなる無機繊維マットは、産業用や住宅用の断熱材や吸音材に広く用いられている。無機繊維マットは、一般に水溶性フェノール樹脂を主成分とするバインダーによって無機繊維同士が固定され、マット状に成形されて製造されている（例えば、特開昭５８−０７０７６０号公報：特許文献１）。 Conventionally, inorganic fiber mats made of inorganic fibers such as glass wool and rock wool have been widely used for industrial and residential heat insulating materials and sound absorbing materials. In general, inorganic fiber mats are manufactured by fixing inorganic fibers to each other with a binder mainly composed of a water-soluble phenol resin and molding the inorganic fibers into a mat shape (for example, JP-A-58-070760: Patent Document 1). .
しかし、上記バインダーの主成分として用いられている水溶性フェノール樹脂は、架橋剤として一般的にホルムアルデヒドが使用されているため、バインダーを加熱硬化する際に、未反応のホルムアルデヒドが無機繊維マットに残留してしまうという問題がある。また、硬化後も、バインダーの加水分解や縮合反応の進行によってホルムアルデヒドが発生するという問題がある。この場合、上記ホルムアルデヒドが、製造後の無機繊維マットの表面や側面から放出されることになる。 However, since the water-soluble phenolic resin used as the main component of the binder generally uses formaldehyde as a cross-linking agent, unreacted formaldehyde remains on the inorganic fiber mat when the binder is cured by heating. There is a problem of end up. Further, even after curing, there is a problem that formaldehyde is generated due to the hydrolysis of the binder and the progress of the condensation reaction. In this case, the formaldehyde is released from the surface and side surfaces of the manufactured inorganic fiber mat.
ホルムアルデヒドのように常温常圧で空気中に容易に揮発する揮発性有機化合物に関して、近年、揮発性有機化合物による室内空気の汚染が顕在化するとともに、揮発性有機化合物が原因のひとつとされるシックハウス症候群などの健康被害が問題となっている。そのため、建築材料からのホルムアルデヒドの放出量が法律で規制されている。よって、建築材料からのホルムアルデヒド及びその他の揮発性有機化合物の放出量を極めて少なくするために、これらの含有量を極めて少なくすることが有効であると考えられる。 Concerning volatile organic compounds that easily volatilize in the air at room temperature and normal pressure, such as formaldehyde, contamination of indoor air by volatile organic compounds has become apparent in recent years, and sick houses are one of the causes of volatile organic compounds. Health damage such as syndrome is a problem. Therefore, the amount of formaldehyde emitted from building materials is regulated by law. Therefore, in order to extremely reduce the amount of formaldehyde and other volatile organic compounds emitted from building materials, it is considered effective to reduce these contents extremely.
無機繊維マットから放出される揮発性有機化合物とは、主にバインダーに含まれるホルムアルデヒドであるため、上記問題点を解決するためには、バインダーに用いる組成物をホルムアルデヒド非含有組成物とする必要がある。しかし、従来のフェノール樹脂を主成分とするバインダーを用いた無機繊維マットは、原料コストが安く、更にマットの復元率や表面強度等が非常に優れたものであった。そのため、ホルムアルデヒド非含有組成物を主成分とするバインダーを用いてもこれらの性能を有する必要があるが、同等の性能を具備させることは困難であった。 Since the volatile organic compound released from the inorganic fiber mat is mainly formaldehyde contained in the binder, the composition used for the binder needs to be a formaldehyde-free composition in order to solve the above problems. is there. However, a conventional inorganic fiber mat using a binder mainly composed of a phenol resin is low in raw material cost, and has a very excellent mat restoration rate, surface strength, and the like. Therefore, it is necessary to have these performances even when using a binder whose main component is a formaldehyde-free composition, but it has been difficult to provide equivalent performance.
上記問題に対応するために、特開２００５−２９９０１３号公報（特許文献２）では、アクリル樹脂系エマルジョンを主成分とするバインダー、また、特開２００６−０８９９０６号公報（特許文献３）では、カルボキシル基等の官能基を持ったビニル共重合体からなるバインダーが提案されている。しかし、これらのバインダーを用いて得られる無機繊維マットの復元率や表面強度等は、水溶性フェノール樹脂を含むバインダーを用いて得られる無機繊維マットと比較して劣るものであった。さらに、本願出願人も特開２０１１−１５３３９５号公報（特許文献４）で、ヒドロキシル基を持つ水溶性高分子化合物とホウ素化合物を含有するバインダーを開示している。しかし、当該バインダーを用いて得られる無機繊維マットは、揮発性有機化合物の問題はクリアできていたものの、水溶性フェノール樹脂に比べて復元率や表面強化度等はやや劣っていた。 In order to cope with the above problem, Japanese Patent Application Laid-Open No. 2005-299013 (Patent Document 2) has a binder mainly composed of an acrylic resin emulsion, and Japanese Patent Application Laid-Open No. 2006-089906 (Patent Document 3) has a carboxyl. A binder made of a vinyl copolymer having a functional group such as a group has been proposed. However, the restoration rate and surface strength of inorganic fiber mats obtained using these binders are inferior to those of inorganic fiber mats obtained using a binder containing a water-soluble phenol resin. Further, the present applicant also discloses a binder containing a water-soluble polymer compound having a hydroxyl group and a boron compound in Japanese Patent Application Laid-Open No. 2011-153395 (Patent Document 4). However, although the inorganic fiber mat obtained using the binder was able to clear the problem of the volatile organic compound, the restoration rate and the degree of surface reinforcement were slightly inferior compared with the water-soluble phenol resin.
国際公開第２００５／０９２８１４号（特許文献５）では無水マレイン酸と不飽和単量体との不飽和共重合物（具体的には無水マレイン酸とブタジエンとの不飽和共重合物）が、特開２０１２−１３６３８５号公報（特許文献６）では無水マレイン酸とアクリル酸エステルの共重合化合物が、特開２０１６−１０８７０７号公報（特許文献７）と特開２０１６−１０８７０８号公報（特許文献８）ではマレイン酸共重合物（メチルビニルエーテル／無水マレイン酸共重合体モノアルキルエステルと思われる）が、特開昭６０−０４６９５１号公報（特許文献９）ではイソブチレン・無水マレイン酸の共重合体が、それぞれ提案されている。無機繊維からなる無機繊維マットは、溶融ガラスに低濃度の水溶性バインダーを噴霧することで製造されるが、前述した化合物等は、いずれも水への溶解度が乏しく、必ずしも好適な水溶性バインダーが得られるものではなかった。 International Publication No. 2005/092814 (Patent Document 5) discloses an unsaturated copolymer of maleic anhydride and an unsaturated monomer (specifically, an unsaturated copolymer of maleic anhydride and butadiene). JP 2012-136385 (Patent Document 6) discloses a copolymer compound of maleic anhydride and an acrylate ester as disclosed in JP-A-2006-108707 (Patent Document 7) and JP-A-2006-108708 (Patent Document 8). Is a maleic acid copolymer (which seems to be a methyl vinyl ether / maleic anhydride copolymer monoalkyl ester), and Japanese Patent Application Laid-Open No. 60-046951 (Patent Document 9) discloses a copolymer of isobutylene and maleic anhydride. Each has been proposed. An inorganic fiber mat made of inorganic fibers is manufactured by spraying a low-concentration water-soluble binder onto molten glass, but all of the above-mentioned compounds have poor solubility in water, and a suitable water-soluble binder is not necessarily used. It was not obtained.
本発明は、上記事情に鑑みなされたもので、揮発性有機化合物の放出が極めて少なく、かつ、十分な厚みと復元性に優れた無機繊維マットを製造することが可能な無機繊維用バインダー、及び該バインダーで処理された無機繊維マットを提供することを目的とする。 The present invention has been made in view of the above circumstances, the binder for inorganic fibers capable of producing an inorganic fiber mat with extremely small release of volatile organic compounds and excellent in sufficient thickness and resilience, and An object is to provide an inorganic fiber mat treated with the binder.
本発明者らは、上記目的を達成するために鋭意検討を行った結果、水溶性高分子化合物と、無水マレイン酸を含有する共重合物のアンモニア変性物とを含有するバインダーが、フェノール樹脂に近い復元率を無機繊維マットに与え、かつ極めて少ない揮発性有機化合物放出量を実現することができることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that a binder containing a water-soluble polymer compound and an ammonia-modified product of a copolymer containing maleic anhydride is added to the phenol resin. The present inventors have found that it is possible to give the inorganic fiber mat a close restoration rate and to realize an extremely small amount of volatile organic compound emission, and to achieve the present invention.
従って、本発明は、下記無機繊維用バインダー及び該バインダーで処理した無機繊維マットを提供する。
〔１〕
（Ａ）水溶性高分子化合物：１００質量部、及び
（Ｂ）無水マレイン酸を含有する共重合物のアンモニア変性物：３質量部以上
を含有することを特徴とする無機繊維用バインダー。
〔２〕
（Ａ）水溶性高分子化合物の重合度が２００〜１，０００である〔１〕記載の無機繊維用バインダー。
〔３〕
（Ａ）水溶性高分子化合物がポリビニルアルコールである〔１〕又は〔２〕記載の無機繊維用バインダー。
〔４〕
（Ｂ）無水マレイン酸を含有する共重合物のアンモニア変性物が、イソブチレン・無水マレイン酸共重合物のアンモニア変性物である〔１〕〜〔３〕のいずれかに記載の無機繊維用バインダー。
〔５〕
上記イソブチレン・無水マレイン酸共重合物のアンモニア変性物が下記式で表される〔４〕記載の無機繊維用バインダー。
〔６〕
無機繊維が、グラスウール又はロックウールである〔１〕〜〔５〕のいずれかに記載の無機繊維用バインダー。
〔７〕
〔１〕〜〔６〕のいずれかに記載の無機繊維用バインダーで処理した無機繊維からなる無機繊維マット。
Accordingly, the present invention provides the following inorganic fiber binder and an inorganic fiber mat treated with the binder.
[1]
(A) Water-soluble polymer compound: 100 parts by mass, (B) Ammonia-modified product of a copolymer containing maleic anhydride: 3 parts by mass or more Binder for inorganic fiber,
[2]
(A) The binder for inorganic fibers according to [1], wherein the degree of polymerization of the water-soluble polymer compound is 200 to 1,000.
[3]
(A) The binder for inorganic fibers according to [1] or [2], wherein the water-soluble polymer compound is polyvinyl alcohol.
[4]
(B) The inorganic fiber binder according to any one of [1] to [3], wherein the ammonia-modified product of the copolymer containing maleic anhydride is an ammonia-modified product of isobutylene / maleic anhydride copolymer.
[5]
The binder for inorganic fibers according to [4], wherein the ammonia-modified product of the isobutylene / maleic anhydride copolymer is represented by the following formula.
[6]
The inorganic fiber binder according to any one of [1] to [5], wherein the inorganic fiber is glass wool or rock wool.
[7]
The inorganic fiber mat which consists of an inorganic fiber processed with the binder for inorganic fibers in any one of [1]-[6].
本発明の無機繊維用バインダーを用いれば、フェノール樹脂に近い復元率を持つ無機繊維マットを作製することができ、またその無機繊維マットからの揮発性有機化合物の放出量は極めて少ない。 If the binder for inorganic fibers of the present invention is used, an inorganic fiber mat having a restoration rate close to that of a phenol resin can be produced, and the amount of volatile organic compounds released from the inorganic fiber mat is extremely small.
以下、本発明を具体的に説明する。
本発明の無機繊維用バインダーは、
（Ａ）水溶性高分子化合物：１００質量部、及び
（Ｂ）無水マレイン酸を含有する共重合物のアンモニア変性物：３質量部以上
を含有するものである。
Hereinafter, the present invention will be specifically described.
The binder for inorganic fibers of the present invention is:
(A) Water-soluble polymer compound: 100 parts by mass, and (B) Ammonia modified product of maleic anhydride-containing copolymer: 3 parts by mass or more.
（Ａ）成分の水溶性高分子化合物は、本発明の無機繊維用バインダーの主剤である。（Ａ）成分の持つ水溶性高分子化合物としては、特に限定されないが、好ましくはポリビニルアルコール、カルボキシメチルセルロース、澱粉などである。これらの中でも、ポリビニルアルコールが特に好ましい。 The water-soluble polymer compound (A) is the main component of the binder for inorganic fibers of the present invention. Although it does not specifically limit as a water-soluble high molecular compound which (A) component has, Preferably they are polyvinyl alcohol, carboxymethylcellulose, starch, etc. Among these, polyvinyl alcohol is particularly preferable.
上記（Ａ）成分の水溶性高分子化合物としては、重合度が１，０００以下のものが好ましく、５００以下のものが更に好ましく、２００〜５００のものが最も好ましい。１，０００を超えると、スプレーによる塗布不良が生じ必要な付着量が得られず無機繊維マットに十分な復元性が得られないなどの不具合が生じる場合がある。上記重合度は、重量平均重合度として、水系ゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析によるポリスチレン換算の値である。また、水溶性高分子化合物のケン化度は、ＪＩＳ Ｋ ６７２６の試験方法に基づいて、８０ｍｏｌ％以上が好ましく、８８ｍｏｌ％以上が更に好ましく、上限値は９９ｍｏｌ％未満であることが好ましい。このケン化度が９９ｍｏｌ％以上であると、低温で粘度上昇が大きくなり、ゲル化することがある。 The water-soluble polymer compound as the component (A) preferably has a polymerization degree of 1,000 or less, more preferably 500 or less, and most preferably 200 to 500. If it exceeds 1,000, defective coating may occur due to spraying and a necessary amount of adhesion cannot be obtained, and sufficient restoration properties cannot be obtained for the inorganic fiber mat. The degree of polymerization is a polystyrene-equivalent value obtained by water-based gel permeation chromatography (GPC) analysis as a weight average degree of polymerization. Further, the saponification degree of the water-soluble polymer compound is preferably 80 mol% or more, more preferably 88 mol% or more, and the upper limit value is preferably less than 99 mol% based on the test method of JIS K 6726. When the degree of saponification is 99 mol% or more, the increase in viscosity becomes large at low temperatures and gelation may occur.
上記（Ａ）成分の水溶性高分子化合物としては、市販品を使用することができ、例えば、日本・酢ビポバール社製の「ポバール（ＰＶＡ）」等が挙げられる。 As the water-soluble polymer compound of the component (A), a commercially available product can be used, and examples thereof include “Poval (PVA)” manufactured by Japan Vinegar Bipoval.
（Ｂ）成分の無水マレイン酸を含有する共重合物のアンモニア変性物は、本発明において架橋剤として機能する。（Ｂ）成分の無水マレイン酸を含有する共重合物のアンモニア変性物としては、特に限定されず、無水マレイン酸とイソブチレン、イソプロピレン、エチレン、エチレン・プロピレン、ブタジエンなどとの共重合物のアンモニア変性物が挙げられる。特に、下記構造式で表されるイソブチレン・無水マレイン酸共重合物のアンモニア変性物が好ましい。
（Ｂ）成分の無水マレイン酸を含有する共重合物のアンモニア変性物の重量平均分子量は、５，０００〜３０，０００が好ましく、１０，０００〜２０，０００が更に好ましく、１５，０００〜２０，０００が最も好ましい。この重量平均分子量は、水系ゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析によるポリスチレン換算の値である。また、上記式中のｎとｍは質量割合を表し、ｎは、ｎ＋ｍの合計１００質量％に対して、０．１〜３質量％が好ましく、０．３〜２質量％が更に好ましく、０．５〜１質量％が最も好ましい。 The weight average molecular weight of the ammonia modified product of the copolymer containing maleic anhydride as the component (B) is preferably from 5,000 to 30,000, more preferably from 10,000 to 20,000, and from 15,000 to 20 Is most preferred. This weight average molecular weight is a value in terms of polystyrene by aqueous gel permeation chromatography (GPC) analysis. In the above formula, n and m represent mass ratios, and n is preferably 0.1 to 3% by mass, more preferably 0.3 to 2% by mass with respect to 100% by mass in total of n + m, 0 0.5 to 1% by mass is most preferable.
（Ｂ）成分の無水マレイン酸を含有する共重合物のアンモニア変性物の含有量は、（Ａ）成分の水溶性高分子化合物１００質量部に対し、３質量部以上であり、好ましくは３〜２０質量部、更に好ましくは３〜５質量部である。無水マレイン酸を含有する共重合物のアンモニア変性物の含有量が３質量部未満であると、架橋性不足などの不具合が生じる場合があり、２０質量部を超えた場合は、（Ａ）成分の水溶性高分子化合物との混和性には問題はないが、処理水溶液が黄色に着色し製品品質低下となり、更にコストアップにも繋がる。 The content of the ammonia-modified product of the copolymer containing maleic anhydride as the component (B) is 3 parts by mass or more, preferably 3 to 100 parts by mass with respect to 100 parts by mass of the water-soluble polymer compound as the component (A). 20 parts by mass, more preferably 3 to 5 parts by mass. When the content of the ammonia-modified product of the copolymer containing maleic anhydride is less than 3 parts by mass, problems such as insufficient crosslinkability may occur. When the content exceeds 20 parts by mass, component (A) There is no problem in miscibility with the water-soluble polymer compound, but the treated aqueous solution is colored yellow, resulting in a decrease in product quality, which further increases costs.
上記（Ｂ）成分の無水マレイン酸含有共重合物としては、市販品を使用することができ、例えば、クラレ社製の「イソバン」等が挙げられる。 A commercially available product can be used as the maleic anhydride-containing copolymer of the component (B), and examples thereof include “Isoban” manufactured by Kuraray Co., Ltd.
更に、本発明の無機繊維用バインダーには、（Ａ）水溶性高分子化合物及び（Ｂ）無水マレイン酸を含有する共重合物のアンモニア変性物以外に、尿素等の保水材、シランカップリング剤、撥水剤、ｐＨ調整剤、着色剤などの添加剤を必要により加えてもよい。これらの添加剤の添加量は、本発明の効果を損なわない範囲で任意とすることができる。 Further, the binder for inorganic fibers of the present invention includes (A) a water-soluble polymer compound and (B) an ammonia-modified product of a copolymer containing maleic anhydride, a water retention material such as urea, and a silane coupling agent. If necessary, additives such as a water repellent, a pH adjuster, and a colorant may be added. The addition amount of these additives can be made arbitrary as long as the effects of the present invention are not impaired.
本発明の無機繊維用バインダーは、水に溶解して無機繊維用バインダー水溶液として使用することが好ましい。上記無機繊維用バインダー水溶液の粘度は、２５℃において１〜１００ｍＰａ・ｓであることが好ましく、特に好ましいのは、１〜５０ｍＰａ・ｓである。なお、この粘度値は、回転粘度計による測定値である。粘度が１００ｍＰａ・ｓを超えると噴霧（吐出）不良となり加工後のバインダー付着量が減少する為、本発明の効果が発揮できない場合がある。また、その濃度は１０質量％以下が好ましく、５質量％以下が更に好ましく、３質量％以下が最も好ましい。 The inorganic fiber binder of the present invention is preferably dissolved in water and used as an inorganic fiber binder aqueous solution. The viscosity of the aqueous binder solution for inorganic fibers is preferably 1 to 100 mPa · s at 25 ° C., and particularly preferably 1 to 50 mPa · s. This viscosity value is a value measured by a rotational viscometer. If the viscosity exceeds 100 mPa · s, spraying (discharge) becomes poor and the amount of binder adhering after processing decreases, so the effects of the present invention may not be exhibited. The concentration is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less.
また、上記無機繊維用バインダー水溶液のｐＨは、４〜８であることが好ましく、４〜６がより好ましい。ｐＨが上記範囲から外れると、架橋性が変化し、復元性に影響を及ぼす場合がある。 Moreover, it is preferable that pH of the said binder aqueous solution for inorganic fibers is 4-8, and 4-6 are more preferable. If the pH deviates from the above range, the crosslinkability may change, affecting the restorability.
本発明の無機繊維用バインダーは、様々な無機繊維に使用可能であり、特にグラスウール、ロックウールに対して優れた効果を発揮する。 The binder for inorganic fibers of the present invention can be used for various inorganic fibers and exhibits an excellent effect particularly on glass wool and rock wool.
本発明の無機繊維マットは、無機繊維を上記無機繊維用バインダーで処理して形成されるものである。上記無機繊維マットに用いられる無機繊維としては、特に限定されないが、グラスウールやロックウールであることが好ましい。 The inorganic fiber mat of the present invention is formed by treating inorganic fibers with the above-mentioned binder for inorganic fibers. Although it does not specifically limit as an inorganic fiber used for the said inorganic fiber mat, It is preferable that they are glass wool and rock wool.
無機繊維の繊維化方法としては、遠心法、吹き飛ばし法など従来公知の方法を採用できる。更に、無機繊維マットの密度も通常の断熱材や吸音材に使用されている密度でよく、好ましくは４０ｋｇ／ｍ3以下、より好ましくは３２ｋｇ／ｍ3以下である。 Conventionally known methods such as a centrifugal method and a blow-off method can be employed as a method for forming inorganic fibers. Further, the density of the inorganic fiber mat may be the density used in ordinary heat insulating materials and sound absorbing materials, and is preferably 40 kg / m 3 or less, more preferably 32 kg / m 3 or less.
無機繊維用バインダーの使用量は、無機繊維に対して固形分比率で１〜１０質量％が好ましく、１〜５質量％がより好ましい。１質量％未満であると、復元性の乏しい無機繊維マットが成形されるなどの不具合が生じる場合があり、１０質量％を超えると、硬く潰れた無機繊維マットが成形されるなどの不具合が生じる場合がある。 The used amount of the binder for inorganic fibers is preferably 1 to 10% by mass, more preferably 1 to 5% by mass in solid content ratio with respect to the inorganic fiber. If it is less than 1% by mass, there may be a problem that an inorganic fiber mat with poor recoverability is formed. If it exceeds 10% by mass, a problem such as forming a hard and crushed inorganic fiber mat occurs. There is a case.
本発明の無機繊維用バインダーを使用して無機繊維マットを製造する方法の一例を、図１及び図２を参照して説明する。図１は、本発明の無機繊維用バインダーを使用して無機繊維マットを製造する工程の一実施形態を示す模式図であり、図２は、本発明の無機繊維用バインダーを無機繊維に付与する工程の一実施形態を示す斜視図である。 One example of a method for producing an inorganic fiber mat using the inorganic fiber binder of the present invention will be described with reference to FIGS. FIG. 1 is a schematic view showing an embodiment of a process for producing an inorganic fiber mat using the inorganic fiber binder of the present invention, and FIG. 2 imparts the inorganic fiber binder of the present invention to the inorganic fiber. It is a perspective view which shows one Embodiment of a process.
まず、繊維化装置１によりグラスウール等の無機繊維を紡出させる繊維化工程が行われる。ここで、繊維化装置１による繊維化の方法としては、特に限定されず、従来公知の遠心法、吹き飛ばし法などが挙げられる。また、繊維化装置１は、製造する無機繊維マット７の密度、厚さ、及び幅方向の長さに応じて複数設けることも可能である。 First, a fiberizing step of spinning inorganic fibers such as glass wool by the fiberizing apparatus 1 is performed. Here, the fiberizing method by the fiberizing apparatus 1 is not particularly limited, and conventionally known centrifugal methods, blow-off methods, and the like can be mentioned. A plurality of fiberizing apparatuses 1 can be provided according to the density, thickness, and length in the width direction of the inorganic fiber mat 7 to be manufactured.
次いで、図２で示すように、バインダー付与装置２によって、繊維化装置１から紡出された無機繊維３に、本発明のバインダーを付与する。バインダーの付与方法としては、従来公知の方法を採用することができ、例えば、上記バインダー水溶液を用いて、スプレー法などで付与することができる。繊維の上層部より直接又は斜め方向から繊維同士の交点部分をメインに交点以外の部分にもバインダーを付着させて処理する。
Next, as shown in FIG. 2, the binder of the present invention is applied to the
コンベア４１は、未硬化のバインダーが付着した無機繊維３を有孔のコンベア上に積層する装置であり、繊維を均一に積層させるために、コンベア４１は吸引装置を有する有孔のコンベアであることが好ましい。
The
ここで、本発明におけるバインダーの付着量とは、強熱減量法又はＬＯＩ（Ｌｏｓｓ ｏｆ Ｉｇｎｉｔｉｏｎ）と呼ばれる方法により測定される量であり、約５５０℃でバインダー付着後の無機繊維マットの乾燥試料を強熱し、減量することにより失われる物質の質量を意味する。 Here, the attached amount of the binder in the present invention is an amount measured by an ignition loss method or a method called LOI (Loss of Ignition), and a dry sample of the inorganic fiber mat after attaching the binder at about 550 ° C. It means the mass of material lost by igniting and losing weight.
上記工程によって、バインダーが付与された無機繊維３は、繊維化装置１の下方に配置されたコンベア４１に堆積され、連続して、ライン方向に沿って設けられているコンベア４２に移動する。そして、コンベア４２及びコンベア４２上に所定間隔で対向配置されたコンベア５によって、堆積した無機繊維３は所定の厚さに圧縮されつつ、コンベア４２、及びコンベア５の位置に配設された成形炉６に入る。
The
成形炉６において、無機繊維３に付与された本発明のバインダーが加熱硬化して、所定の厚さの無機繊維マット７が形成される。なお、加工条件は、ラインの長さ等で大きく変わるため、適宜設定すればよい。例えば、本実施例の場合は、加熱温度は、好ましくは１５０〜３００℃、より好ましくは１８０〜２５０℃である。加熱温度が１５０℃よりも低いと、無機繊維マット７の水分が完全に蒸発しないことがあり、３００℃よりも高いと無機繊維マット７に処理されたバインダーが炭化することがある。また、加熱時間は、好ましくは１２０〜３６０秒、より好ましくは１８０〜３００秒である。加熱温度が１２０秒よりも短いと、無機繊維マット７の水分が完全に蒸発しないことがあり、３６０秒よりも長いと無機繊維マット７に処理されたバインダーが炭化することがある。そして、形成された無機繊維マット７は、コンベア４３の部分に設置された切断機８によって所定の製品寸法に切断された後、コンベア４４によって運ばれ、包装、梱包される。
In the molding furnace 6, the binder of the present invention applied to the
このようにして製造された本発明の無機繊維マットは、フェノール樹脂をはじめとしてこれまで提案されてきたバインダーで処理した無機繊維マットと比較して優れた復元率や表面強度等を持ちながらも、無機繊維マットからの揮発性有機化合物の放出量は極めて少ないものである。 The inorganic fiber mat of the present invention produced as described above has an excellent restoration rate, surface strength, etc. as compared with the inorganic fiber mat treated with a binder that has been proposed so far, including a phenol resin, The amount of volatile organic compounds released from the inorganic fiber mat is extremely small.
なお、ＪＩＳによって、ホルムアルデヒド放散速度は、数段階に区別されている。たとえばＪＩＳ−Ａ９５０４ではＦ☆☆〜Ｆ☆☆☆☆の３段階に区分されており、それぞれ、ホルムアルデヒド放散速度が５μｇ／ｍ2・ｈ以下の場合がＦ☆☆☆☆タイプ、５μｇ／ｍ2・ｈを超えて２０μｇ／ｍ2・ｈ以下の場合がＦ☆☆☆タイプ、２０μｇ／ｍ2・ｈを超えて１２０μｇ／ｍ2・ｈ以下の場合がＦ☆☆タイプである。Ｆ☆☆☆☆タイプが最も優れており、本発明の無機繊維用バインダーを用いた場合、ＪＩＳ−Ａ１９０１のチャンバー法に基づいた試験において、Ｆ☆☆☆☆タイプの無機繊維マットを製造することができる。 According to JIS, the formaldehyde emission rate is classified into several stages. For example, in JIS-A9504, it is divided into three stages of F ☆☆ to F ☆☆☆☆, and when the formaldehyde emission rate is 5 μg / m 2 · h or less, F ☆☆☆☆ type, 5 μg / m 2, respectively. - beyond h 20μg / m 2 · h or less in the case where F ☆☆☆ type, beyond 20 [mu] g / m 2 · h in the following cases 120 [mu] g / m 2 · h is F ☆☆ type. The F ☆☆☆☆ type is the most excellent, and when the inorganic fiber binder of the present invention is used, an F ☆☆☆☆ type inorganic fiber mat is manufactured in a test based on the chamber method of JIS-A1901. Can do.
また、本発明における無機繊維マットの復元率とは、外力を加えて圧縮させた後、外力を除いて復元させた後の無機繊維マットの厚さと、圧縮前の無機繊維マットの厚さの比で表される。無機繊維マットは保管や輸送の効率を上げるために、一定数量以上の無機繊維マットをまとめて圧縮して梱包する場合がある。そのため、開梱して得られる無機繊維マットが圧縮前の厚さを確保できない場合、すなわち、無機繊維マットの復元率が悪い場合には、断熱性や吸音性などの性能が充分に得られない場合がある。 Further, the restoration rate of the inorganic fiber mat in the present invention is the ratio between the thickness of the inorganic fiber mat after being compressed by applying external force and then being restored by removing the external force, and the thickness of the inorganic fiber mat before compression. It is represented by In order to increase the efficiency of storage and transportation of inorganic fiber mats, a certain number or more of inorganic fiber mats may be compressed and packed together. Therefore, when the inorganic fiber mat obtained by unpacking cannot secure the thickness before compression, that is, when the restoration rate of the inorganic fiber mat is poor, performance such as heat insulation and sound absorption cannot be sufficiently obtained. There is a case.
以下、製造例と実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において、部及び％はそれぞれ質量部、質量％を示す。 EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part and% show a mass part and the mass%, respectively.
［実施例１〜４］
表１に記載したポリビニルアルコール１００部とイソブチレン・無水マレイン酸共重合物のアンモニア変性物５部をイオン交換水に溶解し２質量％の濃度である無機繊維用バインダー水溶液を調製した。無機繊維としてグラスウールを用い、調製した無機繊維用バインダー水溶液を用いてスプレー塗布してグラスウールを処理し、実施例における処理条件、２００℃、１８０秒で加熱乾燥して無機繊維マットを作製した。無機繊維マットへの無機繊維用バインダーの処理量は、処理後の無機繊維マットを質量基準として、無機繊維への付着量が無機繊維用バインダーの固形分比率で４％となるようにした。
[Examples 1 to 4]
100 parts of polyvinyl alcohol described in Table 1 and 5 parts of an ammonia-modified product of isobutylene / maleic anhydride copolymer were dissolved in ion-exchanged water to prepare a binder aqueous solution for inorganic fibers having a concentration of 2% by mass. Glass wool was used as the inorganic fiber, and the glass wool was treated by spray coating using the prepared aqueous binder solution for inorganic fiber, and heated and dried at 200 ° C. for 180 seconds under the treatment conditions in the examples to prepare an inorganic fiber mat. The processing amount of the inorganic fiber binder to the inorganic fiber mat was such that the amount of adhesion to the inorganic fiber was 4% in terms of the solid content ratio of the inorganic fiber binder, based on the processed inorganic fiber mat.
［実施例５〜８］
実施例１において、イソブチレン・無水マレイン酸共重合物のアンモニア変性物の量を、それぞれ３部、７部、１０部、２０部とした以外は、実施例１と同様の製造方法により無機繊維用バインダー水溶液を調製し、無機繊維マットを作製した。
[Examples 5 to 8]
In Example 1, the amount of the ammonia-modified product of the isobutylene / maleic anhydride copolymer was changed to 3 parts, 7 parts, 10 parts, and 20 parts, respectively. A binder aqueous solution was prepared to produce an inorganic fiber mat.
［比較例１］
ポリビニルアルコールに代えて、フェノール樹脂「ショーノールＢＲＬ−１０１５」（水溶性フェノール：昭和高分子（株）製）を使用した以外は、実施例１と同様の方法により無機繊維用バインダー水溶液を調製し、無機繊維マットを作製した。
[Comparative Example 1]
A binder aqueous solution for inorganic fibers was prepared in the same manner as in Example 1 except that instead of polyvinyl alcohol, a phenol resin “Shonol BRL-1015” (water-soluble phenol: manufactured by Showa Polymer Co., Ltd.) was used. An inorganic fiber mat was prepared.
［比較例２，３］
実施例１において、無水マレイン酸を含有する共重合物のアンモニア変性物の量をそれぞれ０部、１部とした以外は、実施例１と同様の方法により無機繊維用バインダー水溶液を調製し、無機繊維マットを作製した。
[Comparative Examples 2 and 3]
In Example 1, a binder aqueous solution for inorganic fibers was prepared in the same manner as in Example 1 except that the amounts of ammonia-modified products of the copolymer containing maleic anhydride were 0 parts and 1 part, respectively. A fiber mat was prepared.
［比較例４〜７］
無水マレイン酸を含有する共重合物のアンモニア変性物に代えて、それぞれホウ砂（（株）松葉薬品製）、カルボジライトＶ−０２（カルボジイミド系架橋剤：日清紡（株）製）、メイカネートＴＰ−１２０（イソシアネート系架橋剤：名成化学工業（株）製）、ガントレンツＡＮ−１１９（マレイン酸・メチルビニルエーテル共重合物：五協産業（株）製）を使用した以外は、実施例１と同様の方法により無機繊維用バインダー水溶液を調製し、無機繊維マットを作製した。
[Comparative Examples 4 to 7]
Instead of the ammonia-modified product of the copolymer containing maleic anhydride, borax (manufactured by Matsuba Pharmaceutical Co., Ltd.), Carbodilite V-02 (carbodiimide type cross-linking agent: manufactured by Nisshinbo Co., Ltd.), Meikanate TP-120 (Isocyanate-based cross-linking agent: manufactured by Nasei Chemical Industry Co., Ltd.), Gantrenz AN-119 (maleic acid / methyl vinyl ether copolymer: manufactured by Gokyo Sangyo Co., Ltd.) A binder aqueous solution for inorganic fibers was prepared by the method to prepare an inorganic fiber mat.
［評価方法］
実施例１〜８及び比較例１〜７の無機繊維マットの復元率及びホルムアルデヒド放散速度を測定した。なお、ホルムアルデヒド放散速度はＪＩＳ−Ａ１９０１に基づいて測定した。
[Evaluation method]
The restoration rate and formaldehyde emission rate of the inorganic fiber mats of Examples 1 to 8 and Comparative Examples 1 to 7 were measured. The formaldehyde emission rate was measured based on JIS-A1901.
無機繊維マットの復元率
無機繊維マットの梱包体製造時に、１０ｃｍ×１０ｃｍのサンプルを取り出し、２０ｋｇの加重を１時間かけ、加重後の無機繊維マットの厚み（ｄｘ）を測定し、下記式（１）により復元率を求めた（ｎ＝５）。その結果を表１に併記した。
Ｒ＝（ｄｘ／ｄ）×１００ （１）
Ｒ ：復元率（％）
ｄｘ：復元後の無機繊維マットの厚み（ｍｍ）
ｄ ：試験前の無機繊維マットの呼び厚み（ｍｍ）
Recovery rate of inorganic fiber mat At the time of manufacturing a package of inorganic fiber mat, a sample of 10 cm × 10 cm was taken out, 20 kg of weight was applied for 1 hour, and the thickness (dx) of the inorganic fiber mat after weighting was measured. ) To obtain the restoration rate (n = 5). The results are also shown in Table 1.
R = (dx / d) × 100 (1)
R: Restoration rate (%)
dx: thickness of the inorganic fiber mat after restoration (mm)
d: Nominal thickness (mm) of the inorganic fiber mat before the test
ホルムアルデヒド放散速度
また、無機繊維マットの梱包体を適宜切断し、表面積を４４０ｃｍ2に調整したものを、ホルムアルデヒドの放散速度の測定用試験体とした。ホルムアルデヒド放散速度の測定条件について、測定日数は７日間として、チャンバー内の温度を２８℃、相対湿度を５０％として、チャンバー体積を２０Ｌ、換気回数を１時間当り０．５回とした。サンプリングには、ＤＮＰＨ（２，４−ジニトロフェニルヒドラジン）シリカショートボディ（Ｗａｔｅｒｓ社製）を用いて、捕集体積は１０Ｌとし、捕集流量は１６７ｍＬ／ｍｉｎとした。その結果を表１に併記した。
Formaldehyde emission rate Further , a sample body for measuring the emission rate of formaldehyde was prepared by appropriately cutting an inorganic fiber mat package and adjusting the surface area to 440 cm 2 . Regarding the measurement conditions of the formaldehyde emission rate, the measurement days were 7 days, the temperature in the chamber was 28 ° C., the relative humidity was 50%, the chamber volume was 20 L, and the ventilation frequency was 0.5 times per hour. For sampling, a DNPH (2,4-dinitrophenylhydrazine) silica short body (manufactured by Waters) was used, the collection volume was 10 L, and the collection flow rate was 167 mL / min. The results are also shown in Table 1.
上記表中のポリビニルアルコールの詳細は、下記のとおりである。
・ＪＦ−０５（完全鹸化ポバール：鹸化度９８〜９９％、重合度５００）
・ＪＬ−０５Ｅ（部分鹸化ポバール：鹸化度７８〜８１％、重合度５００）
・ＪＰ−０５（部分鹸化ポバール：鹸化度８７〜８９％、重合度５００）
・ＪＰ−１０（部分鹸化ポバール：鹸化度８７〜８９％、重合度１０００）
上記いずれも日本・酢ビポバール社製
The details of the polyvinyl alcohol in the above table are as follows.
JF-05 (completely saponified poval: saponification degree 98-99%, polymerization degree 500)
JL-05E (partially saponified poval: saponification degree 78-81%, polymerization degree 500)
JP-05 (partially saponified poval: saponification degree 87-89%, polymerization degree 500)
JP-10 (partially saponified PVA: degree of saponification 87-89%, degree of polymerization 1000)
All of the above are manufactured by Japan Vinegar Bipobar
上記表中のイソブチレン・無水マレイン酸共重合物のアンモニア変性物は、「ＩＳＯＢＡＭ−１０４」（株）クラレ製であり、化学構造式は下記のとおりであり、重量平均分子量１６，０００〜１７，０００、ｎ＝０．７〜０．８質量％、ｍ＝９９．２〜９９．３質量％である。
上記表中の無水マレイン酸系共重合物は、「ガントレンツＡＮ−１１９」（無水マレイン酸・メチルビニルエーテル共重合物：五協産業（株）製）である。 The maleic anhydride copolymer in the above table is “Gantrenz AN-119” (maleic anhydride / methyl vinyl ether copolymer: Gokyo Sangyo Co., Ltd.).
１ 繊維化装置
２ バインダー付与装置
３ 無機繊維
４１，４２，４３，４４，５ コンベア
６ 成形炉
７ 無機繊維マット
８ 切断機
DESCRIPTION OF SYMBOLS 1 Fiberizing apparatus 2
Claims (7)
（Ｂ）無水マレイン酸を含有する共重合物のアンモニア変性物：３質量部以上
を含有することを特徴とする無機繊維用バインダー。 (A) Water-soluble polymer compound: 100 parts by mass, (B) Ammonia-modified product of a copolymer containing maleic anhydride: 3 parts by mass or more Binder for inorganic fiber,
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