JP2011208312A - Impregnated paper - Google Patents
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- JP2011208312A JP2011208312A JP2010076924A JP2010076924A JP2011208312A JP 2011208312 A JP2011208312 A JP 2011208312A JP 2010076924 A JP2010076924 A JP 2010076924A JP 2010076924 A JP2010076924 A JP 2010076924A JP 2011208312 A JP2011208312 A JP 2011208312A
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- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004816 latex Substances 0.000 claims abstract description 26
- 229920000126 latex Polymers 0.000 claims abstract description 26
- 239000011256 inorganic filler Substances 0.000 claims abstract description 25
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims description 30
- 230000008859 change Effects 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 46
- 239000000463 material Substances 0.000 abstract description 23
- 238000005470 impregnation Methods 0.000 abstract description 19
- 208000008842 sick building syndrome Diseases 0.000 abstract description 9
- 231100000597 Sick building syndrome Toxicity 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 198
- 238000009408 flooring Methods 0.000 description 36
- 239000010410 layer Substances 0.000 description 27
- 239000011229 interlayer Substances 0.000 description 21
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- 229920001131 Pulp (paper) Polymers 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- 239000003623 enhancer Substances 0.000 description 10
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
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- 239000002245 particle Substances 0.000 description 7
- 239000011120 plywood Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
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- 239000011122 softwood Substances 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000004641 Diallyl-phthalate Substances 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000011094 fiberboard Substances 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000013054 paper strength agent Substances 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
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- 238000009864 tensile test Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229920002401 polyacrylamide Polymers 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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Landscapes
- Paper (AREA)
Abstract
Description
本発明は、含浸紙に関し、特には床材を構成する合板の補強材として用いられる床材用に好適に用いられる含浸紙に関し、より詳細にはシックハウス症候群の原因となるホルムアルデヒドを用いない建材用や床材用等に好適に用いられる含浸紙に関する。 The present invention relates to an impregnated paper, and more particularly to an impregnated paper suitably used for a flooring material used as a reinforcing material for plywood constituting the flooring material, and more particularly for a building material that does not use formaldehyde causing sick house syndrome. The present invention relates to an impregnated paper suitably used for flooring and flooring.
従来より、床材等の建築用化粧板は、一般に化粧シートと、接着剤層と、合板とを具備して構成されている。特に、複合フローリング床材では合板としてベニヤ合板が用いられることが多いが、その補強材として、ＭＤＦ（中密度積層板）が用いられている。しかし、補強材としてＭＤＦが用いられると、合板単体から構成される床材と比べて、コストが高くなるだけでなく、水分を吸収して膨らんでしまい、床面に波打ちが生じ易い、すなわち表面性が悪くなるという問題や耐キャスター性に問題がある。 2. Description of the Related Art Conventionally, an architectural decorative board such as a flooring material is generally provided with a decorative sheet, an adhesive layer, and a plywood. In particular, veneer plywood is often used as the plywood in composite flooring flooring, but MDF (medium density laminated board) is used as the reinforcing material. However, when MDF is used as the reinforcing material, the cost is not only higher than the floor material composed of a single plywood, but it absorbs moisture and swells, and the floor surface is likely to be wavy. There is a problem that the property becomes worse and a problem with caster resistance.
そこで、補強材として、ＭＤＦの他に、例えば特許文献１に示されるような厚さが６０〜３００μｍ程度の樹脂含浸紙硬化層（クラフト紙）や、特許文献２に示されるようなフェノール複合樹脂の液を紙に含浸させたプリプレッグや、特許文献３に示されるような合成樹脂液を塗布した繊維質シートや、特許文献４に示されるような、ＤＡＰ（ジアリルフタレート）樹脂を含浸させた樹脂含浸紙硬化層や、特許文献５に示されるようなメラミン樹脂等を含浸させた樹脂含浸紙基材を使用することが開示されている。 Therefore, as a reinforcing material, in addition to MDF, for example, a resin-impregnated paper cured layer (craft paper) having a thickness of about 60 to 300 μm as shown in Patent Document 1, or a phenol composite resin as shown in Patent Document 2 A prepreg impregnated with a liquid of the above, a fiber sheet coated with a synthetic resin liquid as shown in Patent Document 3, and a resin impregnated with a DAP (diallyl phthalate) resin as shown in Patent Document 4 The use of a resin-impregnated paper base impregnated with a cured impregnated paper layer or a melamine resin as disclosed in Patent Document 5 is disclosed.
このようなクラフト紙等は原紙にフェノール樹脂、メラミン樹脂、ＤＡＰ等の熱硬化性樹脂を含浸塗工することにより、床材の耐衝撃性を維持すると共に、床材の表面に形成される凹凸を被覆し、波打ちが形成されないようにしている。 Such kraft paper is made by impregnating a base paper with a thermosetting resin such as phenol resin, melamine resin, DAP, etc. to maintain the impact resistance of the floor material and to form irregularities formed on the surface of the floor material. So that no waviness is formed.
しかしながら、フェノール樹脂やメラミン樹脂等の熱硬化性樹脂は吸水時の寸法安定性に非常に優れているという利点を有する反面、シックハウス症候群の要因となるホルムアルデヒドを含んでいる。このため、このような含浸紙が床材として用いられると、ホルムアルデヒドが拡散されてシックハウス症候群の原因となるため、環境面、安全面からも脱ホルムアルデヒド化が望まれている。 However, thermosetting resins such as phenol resins and melamine resins have the advantage that they are very excellent in dimensional stability upon water absorption, but contain formaldehyde that causes sick house syndrome. For this reason, when such impregnated paper is used as a flooring, formaldehyde is diffused to cause sick house syndrome, and therefore, formaldehyde removal is desired from the environmental and safety aspects.
また、含浸液の含浸率も高く、薬液を多量に要し、不経済であることや、耐衝撃性をこれら熱硬化性樹脂に頼っているため、クッション性にも限界があり、いまだ耐衝撃性が低いという問題があった。 In addition, the impregnation rate of the impregnating solution is high, requiring a large amount of chemical solution, being uneconomical, and relying on these thermosetting resins for impact resistance, so there is a limit to cushioning properties and still impact resistance There was a problem of low nature.
そこで、ラテックス樹脂などの熱可塑性樹脂を含有する塗工液を含浸または塗工することにより形成した床材用の含浸紙も提案されている。しかしながら、このような床材用の含浸紙は、脱ホルムアルデヒド化を達成することはできるものの、吸水時の膨張が大きい、すなわち寸法安定性が低かったため、含浸紙を床材に加工する際、もしくは床材に加工された完成品において、波打ちや膨れが発生するという問題があった。 Accordingly, an impregnated paper for flooring formed by impregnating or coating with a coating liquid containing a thermoplastic resin such as latex resin has also been proposed. However, although such an impregnated paper for flooring can achieve deformaldehyde formation, the expansion during water absorption is large, that is, the dimensional stability is low, so when the impregnated paper is processed into a flooring, or In the finished product processed into the flooring material, there was a problem that waviness and swelling occurred.
本発明は、上述したような実情に鑑みてなされたもので、その目的とするところは、シックハウス症候群の原因となるホルムアルデヒドを含まず、さらに吸水時の寸法安定性、耐衝撃性、及び層間強度に優れ、床材に好適に用いることができる含浸紙を提供することにある。 The present invention has been made in view of the above-described circumstances, and its object is not to include formaldehyde causing sick house syndrome, and further, dimensional stability at the time of water absorption, impact resistance, and interlayer strength. An object of the present invention is to provide an impregnated paper that can be used suitably for flooring.
本発明の上記目的は、少なくとも熱可塑性樹脂を含む塗工液を、含浸原紙に塗布又は含浸させて形成された含浸紙であって、前記含浸原紙には、原料パルプに対して５〜３０質量％の無機填料と、該無機填料に対して０．１〜５質量％のシランカップリング剤とが内添されており、前記熱可塑性樹脂は、ブタジエン系ラテックス樹脂及び／又はアクリル系ラテックス樹脂であることを特徴とする含浸紙を提供することによって達成される。 The above object of the present invention is an impregnated paper formed by applying or impregnating an impregnated base paper with a coating liquid containing at least a thermoplastic resin. % Inorganic filler and 0.1 to 5% by mass of a silane coupling agent with respect to the inorganic filler are internally added, and the thermoplastic resin is a butadiene latex resin and / or an acrylic latex resin. This is accomplished by providing an impregnated paper characterized in that it is.
また、本発明の上記目的は、前記熱可塑性樹脂の含有量対含浸原紙比が１５〜６０％となるように、前記塗工液を前記含浸原紙に塗布又は含浸し、また、前記含浸原紙は、米坪が７０〜６００ｇ／ｍ２で、かつ、密度が０．４〜０．８５ｇ／ｃｍ３であることを特徴とする含浸紙を提供することによって、効果的に達成される。 In addition, the object of the present invention is to apply or impregnate the coating liquid to the impregnated base paper so that the ratio of the thermoplastic resin content to the impregnated base paper is 15 to 60%. It is effectively achieved by providing an impregnated paper characterized by having a basis weight of 70 to 600 g / m 2 and a density of 0.4 to 0.85 g / cm 3 .
さらにまた、本発明の上記目的は、ＪＩＳ−Ａ５９０５−６−９（２００３）に準じて測定した吸水時の寸法変化率が、厚さ方向で３０％以下であり、且つ、横方向で３％以下であることを特徴とする含浸紙を提供することによって、より効果的に達成される。 Furthermore, the above object of the present invention is such that the rate of dimensional change at the time of water absorption measured in accordance with JIS-A 5905-6-9 (2003) is 30% or less in the thickness direction and 3% in the lateral direction. This is achieved more effectively by providing an impregnated paper characterized by:
本発明に係る含浸紙によれば、原料パルプに対して５〜３０質量％の無機填料と、該無機填料に対して０．１〜５質量％のシランカップリング剤とを内添した含浸原紙に、熱可塑性樹脂としてブタジエン系ラテックス樹脂又はアクリル系ラテックス樹脂を含む塗工液を塗布又は含浸させることにより、無機填料と熱可塑性樹脂とをシランカップリング剤で架橋させることができる。これにより、ホルムアルデヒドが含まれるメラミン樹脂等を含浸させなくても、吸水時に波打ちや膨れの発生を防止し、本発明に係る含浸紙を寸法安定性、耐衝撃性、及び層間強度に優れるものとすることができる。 According to the impregnated paper according to the present invention, an impregnated base paper in which 5 to 30% by mass of an inorganic filler and 0.1 to 5% by mass of a silane coupling agent are internally added to the raw material pulp. Furthermore, the inorganic filler and the thermoplastic resin can be crosslinked with a silane coupling agent by applying or impregnating a coating liquid containing a butadiene latex resin or an acrylic latex resin as the thermoplastic resin. As a result, even without impregnation with melamine resin containing formaldehyde, the occurrence of undulation and swelling during water absorption is prevented, and the impregnated paper according to the present invention has excellent dimensional stability, impact resistance, and interlayer strength. can do.
以下、本発明に係る含浸紙について、床材用に用いられる含浸紙を例にとって詳細に説明する。なお、本発明に係る含浸紙は、以下の実施形態に限定されるものではなく、特許請求の範囲を逸脱しない範囲内において、その構成を適宜変更できることはいうまでもない。 Hereinafter, the impregnated paper according to the present invention will be described in detail by taking the impregnated paper used for flooring as an example. The impregnated paper according to the present invention is not limited to the following embodiments, and it goes without saying that the configuration can be changed as appropriate without departing from the scope of the claims.
本発明に係る含浸紙（以下、「本含浸紙」と言う。）は、含浸原紙（紙基材）に、少なくとも熱可塑性樹脂が含まれる塗工液を塗布又は含浸（以下、「含浸塗布」とも言う。）させて形成される。さらに、本含浸紙の含浸原紙には、無機填料とシランカップリング剤とが内添されており、無機填料の添加量は、含浸原紙の原料パルプ全量に対して５〜３０質量％であり、シランカップリング剤の添加量は、含浸原紙に内添される無機填料の全量に対して０．１〜５質量％である。このように、含浸原紙に無機填料とシランカップリング剤とを内添することにより、無機填料と熱可塑性樹脂とをシランカップリング剤で架橋させることができる。従って、本含浸紙の吸水時におけるパルプの膨張を防止し、吸水時の寸法安定性、耐衝撃性及び層間強度を向上させることができる。すなわち、本発明においては、内添する無機填料やシランカップリング剤、更に熱可塑性樹脂を所定の範囲にて組合わせることで、基本要求品質である耐衝撃性や層間強度を保有するとともに、吸水時の寸法安定性をも向上する相乗効果が得られることを見出している。 The impregnated paper according to the present invention (hereinafter referred to as “the present impregnated paper”) is obtained by applying or impregnating an impregnating base paper (paper base material) with a coating liquid containing at least a thermoplastic resin (hereinafter referred to as “impregnating application”). It is also called.) Furthermore, the impregnated base paper of the present impregnated paper is internally added with an inorganic filler and a silane coupling agent, and the added amount of the inorganic filler is 5 to 30% by mass with respect to the total raw material pulp of the impregnated base paper, The addition amount of the silane coupling agent is 0.1 to 5% by mass with respect to the total amount of the inorganic filler internally added to the impregnated base paper. Thus, by internally adding the inorganic filler and the silane coupling agent to the impregnated base paper, the inorganic filler and the thermoplastic resin can be crosslinked with the silane coupling agent. Therefore, it is possible to prevent the pulp from expanding when the impregnated paper absorbs water, and to improve the dimensional stability, impact resistance and interlayer strength when absorbing water. That is, in the present invention, the inorganic filler and silane coupling agent to be internally added, and the thermoplastic resin are combined in a predetermined range, so that the basic required quality such as impact resistance and interlaminar strength are retained, and water absorption is achieved. It has been found that a synergistic effect that improves the dimensional stability at the time can be obtained.
なお、無機填料の添加量が、含浸原紙の原料パルプ全量に対して５質量％未満であると、吸水時の寸法安定性の向上効果や、耐衝撃性等の強度を向上効果が得られなくなる。一方、３０質量％を超えると抄造時に断紙し易くなると共に、含浸時にも断紙し易くなる為、作業性が低下する。また、シランカップリング剤の添加量が、無機填料の全量に対して０．１質量％未満であると、無機填料と熱可塑性樹脂とを架橋させることが難しくなるため、本願の所望とする吸水時の寸法安定性を得ることが難しくなり、また耐衝撃性等の強度をより向上させる効果を得ることも難しくなる。一方、５質量％を超えると、無機填料と熱可塑性とを架橋させる効果を得ることはできるが、熱可塑性樹脂の特徴である柔らかさが失われるため、本含浸紙が割れ易くなる。 If the amount of the inorganic filler added is less than 5% by mass based on the total amount of raw pulp of the impregnated base paper, the effect of improving the dimensional stability at the time of water absorption and the effect of improving the strength such as impact resistance cannot be obtained. . On the other hand, if it exceeds 30% by mass, it is easy to break the paper at the time of papermaking, and it is easy to break the paper at the time of impregnation, so workability is lowered. Moreover, since it becomes difficult to bridge | crosslink an inorganic filler and a thermoplastic resin as the addition amount of a silane coupling agent is less than 0.1 mass% with respect to the whole quantity of an inorganic filler, the water absorption which this application desires It becomes difficult to obtain dimensional stability at the time, and it is also difficult to obtain an effect of further improving the strength such as impact resistance. On the other hand, if it exceeds 5% by mass, the effect of crosslinking the inorganic filler and the thermoplasticity can be obtained, but the softness characteristic of the thermoplastic resin is lost, so that the impregnated paper is easily broken.
なお、本含浸紙に用いられる無機填料としては、二酸化チタン、シリカゲル、タルク、カオリン、炭酸カルシウム、水酸化アルミニウム、シリカ、焼成クレー、合成ゼオライト等種々のものを、単独で、あるいは２種以上を混合して用いることができる。これらの中でも、二酸化チタン、シリカゲルが用いられると、シランカップリング剤による架橋効果がより向上するため、吸水時のパルプの膨張を抑え、本含浸紙の寸法安定性をより向上させることができる。 As the inorganic filler used in the impregnated paper, various kinds such as titanium dioxide, silica gel, talc, kaolin, calcium carbonate, aluminum hydroxide, silica, calcined clay, synthetic zeolite, alone or in combination of two or more kinds. It can be used by mixing. Among these, when titanium dioxide or silica gel is used, the crosslinking effect by the silane coupling agent is further improved, so that the expansion of the pulp during water absorption can be suppressed, and the dimensional stability of the impregnated paper can be further improved.
また、シランカップリング剤としては、例えば、テトラエトキシシラン、テトラメトキシシラン、メチルトリエトキシシラン、メチルトリメトキシシラン、エチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセトキシシラン、グリシドキシプロピルトリメトキシシラン、アミノプロピルトリメトキシシラン、メルカプトプロピルトリメトキシシラン、オルガノアルコキシシラン等の公知の種々のものを単独で、あるいは２種以上を混合して用いることができる。これらの中でも、得られる含浸紙の吸水時の寸法安定性の向上効果と、含浸紙の基本要求品質である耐衝撃性及び層間強度の保有効果との相乗効果、及び作業性の観点から、オルガノアルコキシシランを用いることが特に好ましい。 Examples of the silane coupling agent include tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, Various known substances such as sidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, mercaptopropyltrimethoxysilane, and organoalkoxysilane can be used alone or in admixture of two or more. Among these, from the viewpoint of the synergistic effect of improving the dimensional stability of the impregnated paper upon water absorption, the basic required quality of the impregnated paper, impact resistance and the effect of retaining interlayer strength, and from the viewpoint of workability, organo It is particularly preferable to use alkoxysilane.
また、本含浸紙に用いられる塗工液は、上述したように、少なくともホルムアルデヒドを含まない熱可塑性樹脂を含有するものである。このようなホルムアルデヒドを含まない熱可塑性樹脂としては、ブタジエン系ラテックス樹脂及び／またはアクリル系ラテックス樹脂が用いられる。このように塗工液に、シックハウス症候群を引き起こすおそれがあるホルムアルデヒドを含むメラミン系樹脂等を含有しないので、本含浸紙が床材として用いられた場合におけるシックハウス症候群の発生を防止することができる。 Moreover, the coating liquid used for this impregnated paper contains the thermoplastic resin which does not contain formaldehyde at least as mentioned above. As such a formaldehyde-free thermoplastic resin, a butadiene latex resin and / or an acrylic latex resin is used. Thus, since the coating liquid does not contain a melamine-based resin containing formaldehyde that may cause sick house syndrome, the sick house syndrome can be prevented from occurring when the impregnated paper is used as a flooring material.
ホルムアルデヒドを含まないブタジエン系ラテックス樹脂としては、スチレン・ブタジエンラテックス（ＳＢＲ）、アクリロニトリル・ブタジエンラテックス（ＮＢＲ）、メチルメタクリレート・ブタジエンラテックス（ＭＢＲ）等が挙げられる。また、ホルムアルデヒドを含まないアクリル系ラテックス樹脂としては、アクリル樹脂、アクリル‐スチレン樹脂、酢酸ビニル樹脂等が挙げられる。これらの中でも、カルボキシ変性ＳＢＲ、アクリレート、未変性ＳＢＲ、変性ＮＢＲ、変性ＭＢＲを用いることが好ましく、特に好ましくはカルボキシ変性ＳＢＲを用いることである。これにより、シランカップリング剤による架橋効果をより得易くなり、本含浸紙の吸水時の寸法安定性をより向上させることができる。さらに、ホルムアルデヒドが含有されていない塗工液を含浸塗布して形成された本含浸紙に優れた耐衝撃性を付与し、さらにまた、耐キャスター性、層間強度及び層間剥離強度を向上させることができるので、本含浸紙の床材としての品質をより優れたものとすることができる。 Examples of the butadiene-based latex resin not containing formaldehyde include styrene / butadiene latex (SBR), acrylonitrile / butadiene latex (NBR), and methyl methacrylate / butadiene latex (MBR). Examples of the acrylic latex resin not containing formaldehyde include acrylic resin, acrylic-styrene resin, and vinyl acetate resin. Of these, carboxy-modified SBR, acrylate, unmodified SBR, modified NBR, and modified MBR are preferably used, and carboxy-modified SBR is particularly preferably used. Thereby, it becomes easier to obtain the crosslinking effect by the silane coupling agent, and the dimensional stability at the time of water absorption of the impregnated paper can be further improved. Furthermore, it can impart excellent impact resistance to the impregnated paper formed by impregnating and applying a coating solution containing no formaldehyde, and can further improve caster resistance, delamination strength and delamination strength. Therefore, the quality of the impregnated paper as a flooring material can be further improved.
また、本含浸紙に用いられる塗工液は、ブタジエン系ラテックス樹脂、アクリル系ラテックス樹脂をそれぞれ単独で用いることもできるが、これら２種類を組み合わせて用いることもできる。２種類を用いる場合においては、ブタジエン系ラテックス樹脂及びアクリル系ラテックス樹脂の混合比率が、ブタジエン系ラテックス樹脂：アクリル系ラテックス樹脂＝２８〜２１％：７２〜７９％であると、本含浸紙の所望とする吸水時の寸法安定性をより得やすくなるとともに、耐衝撃性、耐キャスター性をより向上させることができ、床材用としての品質をより向上させることができる。 Moreover, the coating liquid used for the impregnated paper can be a butadiene latex resin or an acrylic latex resin, but these two types can be used in combination. In the case of using two types, the mixing ratio of the butadiene latex resin and the acrylic latex resin is butadiene latex resin: acrylic latex resin = 28-21%: 72-79%. It becomes easier to obtain the dimensional stability at the time of water absorption, and the impact resistance and caster resistance can be further improved, and the quality for flooring can be further improved.
なお、ブタジエン系ラテックス樹脂の混合比率が２１％未満であると、塗工液の流動性、粘性が低下するため、含浸原紙の紙層内部に塗工液が染み込み過ぎる傾向になり、製造コストが高くなる傾向にある。一方、ブタジエン系ラテックス樹脂の混合比率が２８％を超えると、塗工液の流動性、粘性が上がるため、含浸原紙の紙層内部への塗工液の浸透が低下する傾向になるため、本含浸紙の耐衝撃性の向上効果を得難くなり、また操業性が低下する傾向にある。また、アクリル系ラテックス樹脂の混合比率が７２％未満であると、含浸原紙に塗工液を含浸塗布した後の、含浸紙の層間強度、層間剥離強度の向上効果を得ることが難しくなり、このような含浸紙の床材用としての品質をより向上させる効果を得難くなる。一方、アクリル系ラテックス樹脂の混合比率が７９％を超えると、熱硬化性樹脂を含有しなければ、耐キャスター性、耐衝撃性、層間強度、及び層間剥離強度の向上効果を得難くなる。 If the mixing ratio of the butadiene-based latex resin is less than 21%, the fluidity and viscosity of the coating liquid are reduced, so that the coating liquid tends to soak into the paper layer of the impregnated base paper and the production cost is reduced. It tends to be higher. On the other hand, if the mixing ratio of the butadiene-based latex resin exceeds 28%, the fluidity and viscosity of the coating liquid increase, so that the penetration of the coating liquid into the paper layer of the impregnated base paper tends to decrease. It is difficult to obtain the impact resistance improving effect of the impregnated paper, and the operability tends to be lowered. Further, when the mixing ratio of the acrylic latex resin is less than 72%, it is difficult to obtain an effect of improving the interlaminar strength and delamination strength of the impregnated paper after impregnating and applying the coating liquid to the impregnated base paper. It becomes difficult to obtain the effect of further improving the quality of such impregnated paper for flooring. On the other hand, when the mixing ratio of the acrylic latex resin exceeds 79%, it is difficult to obtain an effect of improving caster resistance, impact resistance, interlayer strength, and delamination strength unless a thermosetting resin is contained.
さらにまた、熱可塑性樹脂のガラス転移温度（Ｔｇ）が−５５〜５０℃、より好ましくは０〜２５℃であると、本含浸紙の耐衝撃性、耐キャスター性、層間強度、及び層間剥離強度の向上効果をより得易くなり、床材用としての品質をより向上させ易くなる。なお、Ｔｇが−５５℃未満であると、機械安定性が悪く、製造時にロール等に皮膜が形成・付着し、実機生産時に悪影響を及ぼす場合がある。一方、Ｔｇが５０℃を超えると、樹脂が硬いため、耐衝撃性をより向上させることが難しくなる。 Furthermore, when the glass transition temperature (Tg) of the thermoplastic resin is −55 to 50 ° C., more preferably 0 to 25 ° C., the impact resistance, caster resistance, interlayer strength, and delamination strength of the impregnated paper are as follows. It becomes easier to obtain the improvement effect of the above, and it becomes easier to improve the quality for flooring. In addition, when Tg is less than -55 ° C, the mechanical stability is poor, and a film is formed and adhered to a roll or the like during production, which may adversely affect actual production. On the other hand, when Tg exceeds 50 ° C., the resin is hard, and it becomes difficult to further improve the impact resistance.
また、本発明に用いられる熱可塑性樹脂は、水溶性ではなく、水分散性がありエマルジョンを形成するものが好ましく、さらに平均粒子径が７５〜４００ｎｍ、より好ましくは１８０〜２３０ｎｍであると、本含浸紙の耐衝撃性、耐キャスター性、層間強度、及び層間剥離強度をより向上させ易くなる。なお、平均粒子径が７５ｎｍ未満であると、エマルジョン粒子の分散性が悪く、エマルジョン粒子が凝集する傾向になり塗工液の塗工性が低下する傾向になる。一方、平均粒子径が４００ｎｍを超えると、塗工液の紙層内部への含浸性が低下するため、層間強度及び層間剥離強度の向上効果を得難く、また操業性が低下する場合もある。 Further, the thermoplastic resin used in the present invention is preferably not water-soluble but water-dispersible and forms an emulsion, and further has an average particle size of 75 to 400 nm, more preferably 180 to 230 nm. It becomes easier to improve the impact resistance, caster resistance, interlayer strength, and delamination strength of the impregnated paper. If the average particle size is less than 75 nm, the dispersibility of the emulsion particles is poor, and the emulsion particles tend to aggregate and the coating properties of the coating liquid tend to decrease. On the other hand, when the average particle diameter exceeds 400 nm, the impregnation property of the coating liquid into the paper layer is lowered, so that it is difficult to obtain an effect of improving the interlayer strength and delamination strength, and the operability may be lowered.
また、本発明に用いられる熱可塑性樹脂は、Ｂ型粘度を１５〜６００ｍＰａ・ｓ、より好ましくは７０〜１００ｍＰａ・ｓとすると、本含浸紙の耐衝撃性、耐キャスター性、層間強度、及び層間剥離強度をより向上させ、本含浸紙の床材用としての品質をより向上させ易くなる。なお、Ｂ型粘度が１５ｍＰａ・ｓ未満であると、塗工液の含浸性は向上するが含浸原紙への定着性が低下するため、熱可塑性樹脂の含有量対含浸原紙比を本願の所望とする範囲に調整し難くなる場合がある。一方、Ｂ型粘度が６００ｍＰａ・ｓを超えると、塗工液の紙層内部への含浸性が低下し、層間強度、層間剥離強度をより向上させる効果が得難くなると共に、操業性も低下する場合がある。 The thermoplastic resin used in the present invention has a B-type viscosity of 15 to 600 mPa · s, more preferably 70 to 100 mPa · s, and impact resistance, caster resistance, interlayer strength, and interlayer The peel strength is further improved, and the quality of the present impregnated paper as a flooring material is easily improved. When the B-type viscosity is less than 15 mPa · s, the impregnation property of the coating liquid is improved, but the fixing property to the impregnated base paper is lowered. Therefore, the ratio of the thermoplastic resin content to the impregnated base paper is determined as desired in the present application. It may be difficult to adjust the range. On the other hand, when the B-type viscosity exceeds 600 mPa · s, the impregnation property of the coating liquid into the paper layer is lowered, and it becomes difficult to obtain the effect of further improving the interlaminar strength and delamination strength, and the operability is also lowered. There is a case.
また、本含浸紙は、上述した塗工液を含浸原紙の全層に含浸塗布することにより形成される。このとき、熱可塑性樹脂の含有量対含浸原紙比が１５〜６０％となるように、含浸原紙に塗工液を含浸塗布することが好ましい。これにより、本含浸紙は、ホルムアルデヒドを含有しなくても、寸法安定性に優れるものとすることができる。 The impregnated paper is formed by impregnating and applying the above-described coating solution to all layers of the impregnated base paper. At this time, it is preferable to impregnate and apply the coating liquid to the impregnated base paper so that the ratio of the thermoplastic resin content to the impregnated base paper is 15 to 60%. Thereby, even if this impregnation paper does not contain formaldehyde, it can be made excellent in dimensional stability.
なお、熱可塑性樹脂の含有量対含浸原紙比が１５％未満であると、シランカップリング剤による架橋効果を得難くなり、本含浸紙が所望とする寸法安定性が得られない場合がある。さらに、本含浸紙の層間強度が低くなり、耐衝撃性が低下するおそれもある。一方、熱可塑性樹脂の含有量対含浸原紙比が６０％を超えると、必要量以上に塗工液が含浸されているため、乾燥に時間が掛かり、作業効率が悪くなるほか、製造コストも高くなる。 When the ratio of the thermoplastic resin content to the impregnated base paper is less than 15%, it is difficult to obtain a crosslinking effect by the silane coupling agent, and the impregnated paper may not obtain the desired dimensional stability. Further, the interlaminar strength of the impregnated paper is lowered, and the impact resistance may be lowered. On the other hand, if the ratio of the thermoplastic resin content to the impregnated base paper exceeds 60%, since the coating liquid is impregnated more than necessary, drying takes time, work efficiency is deteriorated, and production cost is high. Become.
上述したようにして形成された本含浸紙は、床材の品質として要求される耐衝撃性、耐キャスター性、層間強度、及び層間剥離強度をも満足する。すなわち、ＪＩＳ−Ｋ５６００−５−３（１９９９）に記載の「デュポン式衝撃試験」に準拠して測定した衝撃性試験値（以下、「耐衝撃性値」という。）を０．２〜０．７ｍｍ、より好ましくは０．２〜０．６ｍｍとすることができる。耐衝撃性値が０．２ｍｍ未満であると、衝撃を吸収することができず、含浸紙が割れやすい傾向になるため、本含浸紙の床材としての品質を向上させることが難しくなる。一方、耐衝撃性値が０．７ｍｍを超えると、凹み量が大きくなるため、床材としての表面強度を維持できず、同様に本含浸紙を床材としての品質を向上させることが難しくなる。 The impregnated paper formed as described above also satisfies the impact resistance, caster resistance, interlayer strength, and delamination strength required as the quality of the flooring material. That is, the impact test value (hereinafter referred to as “impact resistance value”) measured in accordance with the “DuPont impact test” described in JIS-K5600-5-3 (1999) is 0.2-0. It can be 7 mm, more preferably 0.2 to 0.6 mm. If the impact resistance value is less than 0.2 mm, the impact cannot be absorbed, and the impregnated paper tends to break easily, so that it is difficult to improve the quality of the impregnated paper as a flooring. On the other hand, if the impact resistance value exceeds 0.7 mm, the amount of dents increases, so that the surface strength as a flooring material cannot be maintained, and it becomes difficult to improve the quality of the impregnated paper as a flooring material. .
また、ＪＡＳ合板平面引張試験に準じて測定した剥離時または、破壊時の最大荷重の値（層間強度）を１．０〜２．５ＭＰａ、より好ましくは１．４〜２．３ＭＰａの範囲に調整できる。層間強度は、本発明の好適な用途対象である床材用の含浸紙において基本的な強度指標であり、層間強度が１．０ＭＰａ未満であると、床材用の含浸紙として十分な強度が確保できない問題が生じるおそれがある。一方で層間強度が２．５ＭＰａを超えると、過剰品質であるだけでなく、紙粉や加工適正を悪化させる要因となり得るため好ましくない。 Further, the maximum load value (interlayer strength) at the time of peeling or breaking measured according to the JAS plywood plane tensile test is adjusted to a range of 1.0 to 2.5 MPa, more preferably 1.4 to 2.3 MPa. it can. Interlaminar strength is a basic strength index in impregnated paper for flooring, which is a preferred application object of the present invention. When the interlaminar strength is less than 1.0 MPa, sufficient strength as impregnated paper for flooring is obtained. There is a risk of problems that cannot be secured. On the other hand, if the interlaminar strength exceeds 2.5 MPa, it is not preferable because not only is it an excessive quality, but it can be a factor that deteriorates paper dust and processing suitability.
さらに、ＪＩＳ−Ｋ６１５４−１（１９９９）に準拠して測定した９０度剥離試験値（層間剥離強度）を２００〜１１００ｇ／１５ｍｍとすることができる。なお、層間剥離強度が２００ｇ／１５ｍｍ未満であると、層間強度が下がる、キャスター性が劣るという問題がある。一方、層間剥離強度が１１００ｇ／１５ｍｍを超える床材用含浸紙を製造することは塗工液の濃度の調整等が必要となり、作業性が悪化し、コスト高となる。 Furthermore, the 90 degree peel test value (interlaminar peel strength) measured according to JIS-K6154-1 (1999) can be 200 to 1100 g / 15 mm. In addition, when the delamination strength is less than 200 g / 15 mm, there are problems that the interlaminar strength decreases and caster properties are poor. On the other hand, producing an impregnated paper for flooring having an interlaminar peel strength exceeding 1100 g / 15 mm requires adjustment of the concentration of the coating liquid, resulting in poor workability and high cost.
次に、本含浸紙の紙基材である含浸原紙について説明する。本含浸紙を形成する含浸原紙は、ＪＩＳ−Ｐ８１１８（１９９８）に準じて測定した米坪（以下、「米坪」という。）を７０〜６００ｇ／ｍ２、より好ましくは１３０〜２８０ｇ／ｍ２、さらに密度を０．４〜０．８５ｇ／ｃｍ３、より好ましくは０．６５〜０．７５ｇ／ｃｍ３とすることにより、熱可塑性樹脂の含有量対含浸原紙比を本願の所望とする上記の範囲とすることができる。さらに、本含浸紙の紙基材である含浸原紙をＪＩＳ−Ｐ８２２０に準拠して得られた理解パルプの、ＪＩＳ−Ｐ８１２１（１９９５）に準じて測定した離解フリーネス（以下、「離解フリーネス」という。）が６００〜７００ｃｃとなるように調整することにより、本含浸紙は、耐衝撃性、耐キャスター性、層間強度、及び層間剥離強度により優れたものとなる。ここで、本発明で言う離解フリーネスとは、ＮＢＫＰやＬＢＫＰ、ＴＭＰ等の原料から生成される原料パルプのフリーネスを、叩解や機械的又は物理的分級手段にて調整し、抄紙段階で微細繊維が抜け落ちる等して得られた紙製品段階の原料パルプの特性を指す指標である。 Next, an impregnated base paper that is a paper base material of the impregnated paper will be described. Impregnating a base paper to form a book-impregnated paper, JIS-P8118 (1998) basis weight was measured according to (hereinafter, "basis weight" of.) The 70~600g / m 2, more preferably 130~280g / m 2 Furthermore, the density is set to 0.4 to 0.85 g / cm 3 , more preferably 0.65 to 0.75 g / cm 3 , so that the ratio of the thermoplastic resin to the impregnated base paper is set as desired in the present application. Range. Furthermore, the impregnated base paper, which is the paper base material of the impregnated paper, is a disaggregation freeness (hereinafter referred to as “disaggregation freeness”) of an understanding pulp obtained according to JIS-P8220, measured according to JIS-P8121 (1995). ) Is adjusted to 600 to 700 cc, the impregnated paper becomes more excellent in impact resistance, caster resistance, interlayer strength, and delamination strength. Here, the disaggregation freeness referred to in the present invention refers to adjusting the freeness of raw pulp produced from raw materials such as NBKP, LBKP, and TMP by beating or mechanical or physical classification means, and fine fibers are produced at the papermaking stage. It is an index indicating the characteristics of raw pulp at the paper product stage obtained by falling off.
なお、含浸原紙の米坪が７０ｇ／ｍ２未満であると、含浸原紙（基材）の厚みが薄くなるため緩衝性が劣り、耐衝撃性が低下し、この結果、本含浸紙を床材として使用することが難しくなる。一方、含浸原紙の米坪が６００ｇ／ｍ２を超えると、紙層内の空隙が多くなり、塗工液の含浸性が低くなるため、原料パルプの繊維同士の絡み合いが少なくなり、層間強度が低下するという問題が発生し、同様に本含浸紙を床材用として使用することが難しくなる。また、含浸原紙の密度が０．４ｇ／ｃｍ３未満であると、塗工液が必要量以上に含浸されてしまうため、含浸紙の耐衝撃性が低下すると共に、乾燥に時間が掛かり、作業効率が悪くなるほか、製造コストも高くなるという問題も発生する。一方、密度が０．８５ｇ／ｃｍ３を超えると、塗工液が含浸され難くなるため、熱硬化性樹脂を含有しなければ、本願の所望とする耐キャスター性を満足することが難しくなる。 If the impregnated base paper has a basis weight of less than 70 g / m 2 , the thickness of the impregnated base paper (base material) becomes thin, resulting in poor buffering and impact resistance. As a result, the impregnated paper is used as a flooring material. It becomes difficult to use as. On the other hand, when the basis weight of the impregnated base paper exceeds 600 g / m 2 , voids in the paper layer increase and the impregnation property of the coating liquid decreases, so that the entanglement of the fibers of the raw pulp decreases, and the interlayer strength is reduced. The problem that it falls will generate | occur | produce and it will become difficult to use this impregnated paper for flooring similarly. Further, if the density of the impregnated base paper is less than 0.4 g / cm 3 , the coating liquid is impregnated more than necessary, so that the impact resistance of the impregnated paper is reduced and drying takes time. In addition to the inefficiency, there is a problem that the manufacturing cost increases. On the other hand, when the density exceeds 0.85 g / cm 3 , the coating liquid is difficult to be impregnated. Therefore, if the thermosetting resin is not contained, it is difficult to satisfy the caster resistance desired by the present application.
さらに、含浸原紙の離解フリーネスが６００ｃｃ未満であると、塗工液の含浸性が低くなるため、含浸紙の層間強度、層間剥離強度をより向上させることが難しくなる。一方、離解フリーネスが７００ｃｃを超えると、含浸原紙の地合が悪くなるため、塗工液が含浸原紙に均一に含浸されず、塗工液の含浸性が阻害されてしまう。このため、本含浸紙の塗工液の含浸性が低くなるため、同様に、層間強度、層間剥離強度をより向上させることが難しくなる。 Furthermore, when the disaggregation freeness of the impregnated base paper is less than 600 cc, the impregnation property of the coating liquid is lowered, and it is difficult to further improve the interlayer strength and delamination strength of the impregnated paper. On the other hand, when the disaggregation freeness exceeds 700 cc, the formation of the impregnated base paper is deteriorated, so that the impregnating base paper is not uniformly impregnated with the impregnating raw paper, thereby impairing the impregnation property of the coating liquid. For this reason, since the impregnation property of the coating liquid of this impregnated paper becomes low, similarly, it becomes difficult to further improve the interlayer strength and the delamination strength.
また、本含浸紙に用いられる含浸原紙を構成する各層の原料パルプには、広葉樹晒クラフトパルプ（ＬＢＫＰ）、針葉樹晒クラフトパルプ（ＮＢＫＰ）、広葉樹未晒クラフトパルプ（ＬＵＫＰ）、針葉樹未晒クラフトパルプ（ＮＵＫＰ）、広葉樹亜硫酸パルプ、針葉樹亜硫酸パルプ等の木材繊維を主原料として、化学的に処理されたパルプ、化学的に処理されたパルプやチップを機械的にパルプ化したグランドパルプ、さらに、加温、加圧下でチップを機械的にパルプ化したサーモメカニカルパルプ（ＴＭＰ）、木材またはチップに化学薬品を添加しながら機械的にパルプ化したケミグランドパルプ、及びチップを柔らかくなるまで蒸解した後、レファイナー等でパルプ化したセミケミカルパルプ等のバージンパルプ等を用いることができる。また、木材以外の繊維原料であるケナフ、麻、葦等の非木材繊維も用いることができるが、非木材パルプはパルプ強度が弱く、パルプ自体の単価が高いため、コストも高くなることからＮＢＫＰなどのクラフトパルプ、ＴＭＰなどの機械パルプを用いることが好ましい。 The raw material pulp of each layer constituting the impregnated base paper used for the impregnated paper includes hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP), and softwood unbleached kraft pulp (NUKP), hardwood sulfite pulp, softwood sulfite pulp and other wood fibers as the main raw material, chemically treated pulp, chemically treated pulp and ground pulp mechanically pulped chips, Thermo-mechanical pulp (TMP) that mechanically pulped chips under temperature and pressure, Chemi-ground pulp mechanically pulped with chemicals added to wood or chips, and after cooking the chips until soft, Virgin pulp such as semi-chemical pulp pulped with a refiner etc. can be usedIn addition, non-wood fibers such as kenaf, hemp, and straw, which are fiber materials other than wood, can be used. However, non-wood pulp has low pulp strength and the unit price of the pulp itself is high. It is preferable to use mechanical pulp such as kraft pulp and TMP.
これらの中でも特に、含浸原紙を構成する原料パルプの好適な原料配合は、針葉樹晒クラフトパルプ（ＮＢＫＰ）が５〜５０質量％、好ましくは１０〜４０質量％、より好ましくは１０〜３０質量％であり、広葉樹晒クラフトパルプ（ＬＢＫＰ）が５０〜９５質量％、好ましくは６０〜９０質量％であり、機械パルプ（ＴＭＰ）が０〜２０質量％、好ましくは０〜１０質量％である。これにより、本含浸紙の所望とする耐衝撃性、層間強度を保有することができると共に、吸水時の寸法安定性をも向上させるという相乗効果をより得易くなる。さらに、離解フリーネスの調整を行い易くなると共に、熱可塑性樹脂の含浸性をより向上させることもできる。 Among these, the suitable raw material composition of the raw material pulp constituting the impregnated base paper is 5 to 50% by mass, preferably 10 to 40% by mass, more preferably 10 to 30% by mass of softwood bleached kraft pulp (NBKP). Yes, hardwood bleached kraft pulp (LBKP) is 50 to 95 mass%, preferably 60 to 90 mass%, and mechanical pulp (TMP) is 0 to 20 mass%, preferably 0 to 10 mass%. As a result, the desired impact resistance and interlayer strength of the impregnated paper can be retained, and a synergistic effect of improving the dimensional stability during water absorption can be obtained more easily. Furthermore, the disaggregation freeness can be easily adjusted, and the impregnation property of the thermoplastic resin can be further improved.
なお、ＮＢＫＰの配合率が５０質量％を超えると、地合いが悪くなり、含浸性が劣る傾向になる。一方、ＮＢＫＰの配合率が５質量％未満になると、本含浸紙の層間強度、層間剥離強度が低くなり、層間剥離を起こしやすくなるため、本含浸紙を床材として使用することが難しくなる。また、ＴＭＰなどの機械パルプの配合率が２０質量％を超えると、機械パルプ特有の樹脂分が多くなるので、熱可塑性樹脂の浸透性が低下する傾向になり、上述した本願の所望とする熱可塑性樹脂の含有量対含浸原紙比を確保することが難しくなる。この結果、本含浸紙の耐衝撃性、層間強度、層間剥離強度が低下するおそれがある。 In addition, when the compounding ratio of NBKP exceeds 50% by mass, the texture is deteriorated and the impregnation property tends to be inferior. On the other hand, when the blending ratio of NBKP is less than 5% by mass, the interlaminar strength and delamination strength of the impregnated paper are lowered, and delamination is likely to occur, making it difficult to use the impregnated paper as a flooring material. Further, when the blending ratio of mechanical pulp such as TMP exceeds 20% by mass, the resin content peculiar to mechanical pulp increases, so that the permeability of the thermoplastic resin tends to decrease, and the desired heat of the present application described above. It becomes difficult to ensure the ratio of the content of the plastic resin to the impregnated base paper. As a result, the impact resistance, interlayer strength, and delamination strength of the impregnated paper may be reduced.
なお、古紙からなるパルプを配合しても良いが、微細繊維が多いため、含浸原紙の濾水性が悪くなり、生産スピードが落ち、また塗工液を含浸原紙に含浸させた後の紙面の見栄えが悪化するとともに、層間強度も低下してしまう。従って、古紙パルプは特に表層及び裏層を形成する原料パルプには配合しない方が好ましく、また中層を形成する原料パルプにも配合しないほうがより好ましい。さらに、本含浸紙は含浸原紙に樹脂を含浸させて構成するので、同じ配合の原料パルプを用いて各層を抄造するのが好ましいが、表層、中層、裏層と異なる配合の原料パルプを用いて抄紙しても良い。 Although pulp made from waste paper may be blended, because there are many fine fibers, the drainage of the impregnated base paper deteriorates, the production speed decreases, and the appearance of the paper after the impregnating base paper is impregnated with the coating liquid Deteriorates and the interlaminar strength also decreases. Therefore, it is preferable not to mix the waste paper pulp with the raw material pulp that forms the surface layer and the back layer, and it is more preferable not to mix it with the raw material pulp that forms the middle layer. Furthermore, since the impregnated paper is constituted by impregnating the impregnated base paper with a resin, it is preferable to make each layer using raw pulp of the same composition, but using raw pulp of a composition different from the surface layer, middle layer, and back layer You may make paper.
また、含浸原紙の少なくとも１層の原料パルプ中に、湿潤紙力増強剤及び乾燥紙力増強剤を添加することが好ましい。これにより、塗工液の含浸塗布時の加工適性を向上させることができると共に、本含浸紙の層間強度をより高くすることができる。さらには、含浸原紙を構成する全層の原料パルプ中に湿潤紙力増強剤及び乾燥紙力増強剤を添加することがより好ましい。 Moreover, it is preferable to add a wet paper strength enhancer and a dry paper strength enhancer to at least one layer of raw pulp of the impregnated base paper. Thereby, the processability at the time of the impregnation application of the coating liquid can be improved, and the interlayer strength of the impregnated paper can be further increased. Further, it is more preferable to add a wet paper strength enhancer and a dry paper strength enhancer to the raw pulp of all layers constituting the impregnated base paper.
このような湿潤紙力増強剤としては、例えばポリアミドポリアミン・エピクロロヒドリン系，メラミン・ホルマリン系，尿素・ホルマリン系樹脂等を用いることができる。また、乾燥紙力増強剤としては、アニオンまたはカチオンまたは両性のポリアクリルアミド、ポリビニルアルコール、カチオン化澱粉、植物性ガラクトマンナン等を用いることができる。しかしながら、本含浸紙に用いられる湿潤紙力増強剤、乾燥紙力増強剤はこれらに限定されるものではない。 As such a wet paper strength enhancer, for example, polyamide polyamine / epichlorohydrin type, melamine / formalin type, urea / formalin type resin and the like can be used. Moreover, as a dry paper strength enhancer, anionic or cationic or amphoteric polyacrylamide, polyvinyl alcohol, cationized starch, vegetable galactomannan and the like can be used. However, the wet paper strength enhancer and the dry paper strength enhancer used for the impregnated paper are not limited to these.
上記の紙力増強剤を添加することにより、含浸原紙の塗工液の含浸性が低下してしまうため、紙力増強剤を添加した原料パルプには消サイズ剤を添加することがより好ましい。また、含浸原紙に塗工液の含浸性を付与するために、消サイズ剤の他に吸液剤や嵩高剤等の薬品を添加することも可能である。なお、原料パルプの叩解の度合いや、パルプの配合率によっては消サイズ剤等の薬品を添加する必要がないので、この場合には添加しなくても良い。 By adding the paper strength enhancer, the impregnation property of the coating liquid of the impregnated base paper is deteriorated. Therefore, it is more preferable to add a sizing agent to the raw material pulp to which the paper strength enhancer is added. Further, in order to impart the impregnating property of the coating liquid to the impregnated base paper, it is possible to add chemicals such as a liquid absorbing agent and a bulking agent in addition to the sizing agent. In addition, since it is not necessary to add chemicals, such as a sizing agent, depending on the degree of beating of the raw pulp and the blending ratio of the pulp, it is not necessary to add in this case.
なお、含浸原紙を構成する各層の原料パルプに添加される薬品の添加量、種類等については適宜調整することができる。 In addition, about the addition amount of a chemical | medical agent added to the raw material pulp of each layer which comprises an impregnation base paper, a kind, etc. can be adjusted suitably.
上述した原料パルプは、公知の抄紙工程、例えばワイヤーパート、プレスパート、ドライヤーパート、サイズプレス、カレンダーパートなどを経て、好ましくは３〜４層の紙層を有する含浸原紙を形成する。なお、含浸原紙の抄紙方法については、特に限定されるものではないので、酸性抄紙法、中性抄紙法、アルカリ性抄紙法のいずれであっても良い。また、抄紙機も特に限定されるものではないので、例えば長網抄紙機、ツインワイヤー抄紙機、円網抄紙機、円網短網コンビネーション抄紙機等の公知の種々の抄紙機を使用することができる。 The raw material pulp described above forms an impregnated base paper preferably having 3 to 4 paper layers through a known papermaking process, for example, a wire part, a press part, a dryer part, a size press, a calendar part, and the like. The paper making method of the impregnated base paper is not particularly limited, and any of acid paper making method, neutral paper making method and alkaline paper making method may be used. Also, since the paper machine is not particularly limited, for example, various known paper machines such as a long net paper machine, a twin wire paper machine, a circular net paper machine, and a short net combination machine can be used. it can.
こうして形成された含浸原紙は、塗工液の樹脂含浸性が０．５〜３．０秒、より好ましくは０．７〜１．２秒であると、熱可塑性樹脂の含有量対含浸原紙比を上述した１５〜６０％に調整することがより容易となる。 The impregnated base paper formed in this way has a resin impregnating property of the coating liquid of 0.5 to 3.0 seconds, more preferably 0.7 to 1.2 seconds. Is more easily adjusted to 15 to 60% described above.
上述したように、無機填料とシランカップリング剤とが内添された含浸原紙に、熱可塑性樹脂が含まれる塗工液を含浸塗布させて形成された本含浸紙は、ＪＩＳ−Ａ５９０５−６−９（２００３）に準じて測定した吸水厚さ膨張率（以下、「寸法変化率」と言う。）を、厚さ方向で３０％以下とし、且つ横方向で３％以下とすることができる。すなわち、本含浸紙は、無機填料と熱可塑性樹脂とをシランカップリング剤により架橋させることにより、ホルムアルデヒドを含有させることなく、吸水時の寸法安定性に優れるものとなる。なお、寸法変化率が厚さ方向で３０％を超えると、含浸紙が水分を吸水し、膨張してしまうため、このような含浸紙が床材として用いられると、いわゆる膨れが発生する。また、寸法変化率が横方向で３％を超えると、このような含浸紙が床材に用いられた場合、床材が吸水して波打ち等が発生する。 As described above, this impregnated paper formed by impregnating and applying a coating liquid containing a thermoplastic resin to an impregnated base paper in which an inorganic filler and a silane coupling agent are internally added is JIS-A5905-6. 9 (2003), the water absorption thickness expansion coefficient (hereinafter referred to as “dimensional change rate”) can be 30% or less in the thickness direction and 3% or less in the lateral direction. That is, the present impregnated paper is excellent in dimensional stability at the time of water absorption without containing formaldehyde by crosslinking the inorganic filler and the thermoplastic resin with a silane coupling agent. If the rate of dimensional change exceeds 30% in the thickness direction, the impregnated paper absorbs moisture and expands. Therefore, when such impregnated paper is used as a flooring, so-called swelling occurs. Further, when the dimensional change rate exceeds 3% in the lateral direction, when such impregnated paper is used for the flooring, the flooring absorbs water and undulations occur.
以上に詳述したように、本含浸紙は、無機填料とシランカップリング剤とを内添した含浸原紙に、ホルムアルデヒドを含まない熱可塑性樹脂を含有させて形成するので、無機填料と熱可塑性樹脂とをシランカップリング剤によって架橋することができる。これにより、脱ホルムアルデヒド化を達成することができ、シックハウス症候群を防止することができると共に、寸法安定性に優れるものとすることができる。さらに、本含浸紙は、ホルムアルデヒドを含有しなくても床材として要求される耐衝撃性、耐キャスター性、層間強度、及び層間剥離強度を満足させることができる。 As described in detail above, this impregnated paper is formed by adding a formaldehyde-free thermoplastic resin to an impregnated base paper internally added with an inorganic filler and a silane coupling agent. Can be crosslinked by a silane coupling agent. As a result, formaldehyde removal can be achieved, sick house syndrome can be prevented, and dimensional stability can be improved. Furthermore, the impregnated paper can satisfy the impact resistance, caster resistance, interlayer strength, and delamination strength required as a flooring material even without containing formaldehyde.
本発明に係る含浸紙の効果を確認するため、以下のような各種の試料を作製し、これらの各試料に対する品質を評価する試験を行った。なお、本実施例において、配合、濃度等を示す数値は、固形分又は有効成分の質量基準の数値である。また、本実施例で示すパルプ・薬品等は一例にすぎないので、本発明はこれらの実施例によって制限を受けるものではなく、適宜選択可能であることはいうまでもない。 In order to confirm the effect of the impregnated paper according to the present invention, the following various samples were prepared, and a test for evaluating the quality of each sample was performed. In addition, in a present Example, the numerical value which shows a mixing | blending, a density | concentration, etc. is a numerical value of solid content or the mass reference | standard of an active ingredient. Moreover, since the pulp, chemical | medical agent, etc. which are shown in a present Example are only examples, it cannot be overemphasized that this invention is not restrict | limited by these Examples, and can be selected suitably.
本発明に係る５７種類の含浸紙（これを「実施例１」ないし「実施例５７」とする）と、これらの実施例１ないし実施例５７と比較検討するために、６種類の含浸紙（これを「比較例１」ないし「比較例６」とする）を、表１及び表２に示すような構成で作製した。 57 kinds of impregnated papers (referred to as “Example 1” to “Example 57”) according to the present invention and six kinds of impregnated papers (for comparison with these Examples 1 to 57) ( This was referred to as “Comparative Example 1” to “Comparative Example 6”) and produced in the configurations shown in Tables 1 and 2.
〔実施例１〕
＜原料＞
含浸紙を構成する含浸原紙を、表１に示すように作製した。
すなわち、表１に示すように、針葉樹晒クラフトパルプ（ＮＢＫＰ）１０質量％と、広葉樹晒クラフトパルプ（ＬＢＫＰ）９０質量％とを配合した後に、ＪＩＳ−Ｐ８１２１（１９９５）に準じて測定した離解フリーネスが６００ｃｃになるように調整した原料に、無機填料としてシリカゲルを原料パルプ全量に対して５質量％と、シランカップリング剤としてオルガノアルコキシシランを、無機填料全量に対して５質量％とを内添し、さらに湿潤紙力剤（星光ＰＭＣ株式会社製ＷＳ４０２４）を有姿で０．５質量％（５ｋｇ／ｔ）、乾燥紙力剤（星光ＰＭＣ株式会社製ＤＳ４３５６）を有姿で０．４質量％（４ｋｇ／ｔ）配合して、表層、中層及び裏層用の原料パルプスラリーを得た。これらの原料パルプスラリーを用い、円網抄紙機にて表層、１層の中層、及び裏層の紙層を抄き合わせて、表層の付け量を４６ｇ／ｍ２、中層の付け量を４８ｇ／ｍ２、裏層の付け量を４６ｇ／ｍ２、含浸原紙全体の坪量（米坪）が１４０ｇ／ｍ２である３層抄きの含浸原紙を得た。
＜塗工液＞
この含浸原紙に含浸塗布する塗工液を、表２に示すように作製した。すなわち、熱可塑性樹脂として、カルボキシ変性ＳＢＲ（日本エイアンドエル株式会社製 ＳＲ１０２ Ｔｇ：２１℃）を含有させた塗工液を得た。
＜含浸紙の作成＞
上記含浸原紙に、ディッピングスクイズ式含浸機を用いて、表３に示すように熱可塑性樹脂の含有量対含浸原紙比が４８％となるように、上述した塗工液を含浸原紙に含浸塗布させて、含浸紙（実施例１）を作成する。
[Example 1]
<Raw material>
The impregnated base paper constituting the impregnated paper was prepared as shown in Table 1.
That is, as shown in Table 1, after blending 10% by weight of softwood bleached kraft pulp (NBKP) and 90% by weight of hardwood bleached kraft pulp (LBKP), the disaggregation freeness measured according to JIS-P8121 (1995). To the raw material adjusted to 600 cc, silica gel as the inorganic filler is 5% by mass with respect to the total amount of the raw material pulp, organoalkoxysilane as the silane coupling agent, and 5% by mass with respect to the total amount of the inorganic filler. In addition, 0.5% by mass (5 kg / t) of wet paper strength agent (WS4024 manufactured by Seiko PMC Co., Ltd.) and 0.4 mass of dry paper strength agent (DS4356 manufactured by Seiko PMC Co., Ltd.). % (4 kg / t) was blended to obtain a raw material pulp slurry for the surface layer, middle layer and back layer. Using these raw material pulp slurries, the surface layer, the middle layer, and the back layer paper layer are made together by a circular paper machine, the surface layer weight is 46 g / m 2 , and the middle layer weight is 48 g / m. m 2, 46g / m 2 Paste amount of backing layer, the basis weight of the entire impregnated base paper (basis weight) was obtained impregnated sheet of paper making 3-layer is 140 g / m 2.
<Coating fluid>
A coating solution for impregnating and coating the impregnated base paper was prepared as shown in Table 2. That is, as a thermoplastic resin, a coating solution containing carboxy-modified SBR (SR102 Tg: 21 ° C., manufactured by Nippon A & L Co., Ltd.) was obtained.
<Preparation of impregnated paper>
Using the dipping squeeze type impregnation machine, impregnating the above impregnated base paper with the above-mentioned coating solution so that the ratio of the thermoplastic resin content to the impregnated base paper is 48% as shown in Table 3. Thus, impregnated paper (Example 1) is prepared.
また、実施例２〜５７、及び比較例１〜６を表１、表２、及び表３の熱可塑性樹脂の含有量対含浸原紙比の欄に示す条件以外は実施例１と同様に含浸紙を作製した。なお、表１中の無機填料の二酸化チタンとしてタイペークＷ−１０（石原産業社製）を用い、タルクとして体積平均粒子径１２μｍのエリエールケミカル社製のものを用い、カオリンとしてハイドラグロス９０（ＨＵＢＥＲ社製）を用い、炭酸カルシウムとしてＴＰ−１２１（奥多摩工業製）を用い、水酸化アルミニウムとしてレーザー回析法による中心粒子径が１．０μｍの水酸化アルミニウム（日本軽金属社製）を用い、シリカとしてエリエールケミカル社製のレーザー回析法による中心粒子径が１８μｍのホワイトカーボンを用い、焼成クレーとして白石カルシウム社製のＫＡＯＣＡＬを用いた。また、表１中のシランカップリング剤のビニルトリメトキシシランとして信越シリコーン社製のＫＢＭ−１００３を用い、メチルトリメトキシシランとして（株）タナック社製のＴＳＬ８１１３を用い、テトラメトキシシランとして東横化学社製を用い、エチルトリエトキシシランとして信越シリコーン社製を用い、テトラエトキシシランとして東横化学社製を用いた。 Further, Examples 2 to 57 and Comparative Examples 1 to 6 were impregnated in the same manner as in Example 1 except for the conditions shown in the column of thermoplastic resin content to impregnated base paper ratio in Tables 1, 2 and 3. Was made. In addition, as the inorganic filler titanium dioxide in Table 1, Typeke W-10 (manufactured by Ishihara Sangyo Co., Ltd.) is used. TP-121 (manufactured by Okutama Kogyo) as calcium carbonate, aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd.) having a center particle size of 1.0 μm as aluminum hydroxide, and silica as White carbon having a center particle diameter of 18 μm by a laser diffraction method manufactured by Ellere Chemical Co. was used, and KAOCAL manufactured by Shiraishi Calcium Co. was used as a calcined clay. Further, KBE-1003 manufactured by Shin-Etsu Silicone Co., Ltd. is used as the vinyltrimethoxysilane of the silane coupling agent in Table 1, TSL8113 manufactured by Tanac Corporation is used as methyltrimethoxysilane, and Toyoko Chemical Co., Ltd. is used as tetramethoxysilane. Manufactured by Shin-Etsu Silicone Co., Ltd. was used as ethyltriethoxysilane, and Toyoko Chemical Co., Ltd. was used as tetraethoxysilane.
また、表２中の未変性カルボキシＳＢＲ（表中では、「未変性ＳＢＲ」と記す。）として、日本ゼオン株式会社製の２５０７Ｈ（Ｔｇ：５８℃）を用い、変性ＮＢＲとして日本エイアンドエル株式会社製のＮＡ−２０（Ｔｇ：−２０℃）を用い、また、変性ＭＢＲとして日本エイアンドエル株式会社製のＭＲ−１７１（Ｔｇ：−３０℃）を用い、またアクリレートとして星光ＰＭＣ株式会社製のＸＰ８８０６（Ｔｇ：０℃）を用い、メラミンとして、日本カーバイド株式会社製のＳ−２６０を用いた。 In addition, 2507H (Tg: 58 ° C.) manufactured by Zeon Corporation was used as the unmodified carboxy SBR in Table 2 (referred to as “unmodified SBR” in the table), and Nippon A & L Co., Ltd. was used as the modified NBR. NA-20 (Tg: −20 ° C.), MR-171 (Tg: −30 ° C.) manufactured by Nippon A & L Co., Ltd. as the modified MBR, and XP8806 (Tg manufactured by Seiko PMC Co., Ltd.) as the acrylate. : 0 ° C.), and S-260 manufactured by Nippon Carbide Corporation was used as the melamine.
なお、表１中の「離解フリーネス（ｃｃ）」とは、ＪＩＳ−Ｐ８１２１（１９９５）に記載の「紙及び板紙−パルプのろ水度試験方法−カナダ標準ろ水度試験方法」に準拠して測定した値である。 “Disaggregation freeness (cc)” in Table 1 refers to “paper and paperboard—pulp freeness test method—Canadian standard freeness test method” described in JIS-P8121 (1995). It is a measured value.
また、「米坪（ｇ／ｍ２）」とは、各試料全層、すなわち床材用含浸紙に用いられる紙基材全体の坪量で、ＪＩＳ−Ｐ８１２４（１９９８）に記載の「紙及び板紙−坪量測定方法」に準拠して測定した値である。 Further, “US basis weight (g / m 2 )” is the basis weight of the entire paper base material used for all layers of each sample, that is, the impregnated paper for flooring, and “paper and paper” described in JIS-P8124 (1998). It is the value measured based on "paperboard-basis weight measuring method".
「密度（ｇ／ｃｍ３）」とは、ＪＩＳ−Ｐ８１２４（１９９８）に記載の「紙及び板紙−坪量測定方法」に準拠して測定した坪量と、ＪＩＳ−Ｐ８１１８（１９９８）に記載の「紙及び板紙−厚さ及び密度の試験方法」に準拠して測定した紙厚から算出した値である。 “Density (g / cm 3 )” refers to the basis weight measured in accordance with “Paper and paperboard—basis weight measurement method” described in JIS-P8124 (1998) and JIS-P8118 (1998). It is a value calculated from the paper thickness measured according to “Paper and paperboard—Test method of thickness and density”.
「剥離強度（ＭＰａ）」とは、含浸原紙の層間強度を評価したもので、ＪＩＳ−Ｐ８１３１（１９９５）に記載の「紙及び板紙−ミューレン高圧形試験機による破裂強さ試験方法に準拠して測定した値である。 “Peel strength (MPa)” is an evaluation of the interlaminar strength of the impregnated base paper. According to “Paper and paperboard—Murlen high-pressure type tester based on burst strength test method” described in JIS-P8131 (1995). It is a measured value.
「樹脂浸透性（秒）」とは、塗工液の吸液時間を評価したもので、上記吸油度の測定方法で使用するキット６液の代わりに、カルボキシ変性ＳＢＲ（日本エイアンドエル（株）製 ＳＲ１０２ Ｔｇ：２１℃）を使用して測定した値である。 “Resin permeability (seconds)” is an evaluation of the liquid absorption time of the coating liquid. Instead of the kit 6 liquid used in the oil absorption measurement method, carboxy-modified SBR (manufactured by Nippon A & L Co., Ltd.) SR102 Tg: 21 ° C.).
これらの全実施例及び比較例の含浸紙について品質評価を行った結果は、表３に示すとおりであった。なお、この品質評価試験は、ＪＩＳ−Ｐ８１１１に準拠して温度２３±２℃、湿度５０±２％の環境条件で行った。 Table 3 shows the results of quality evaluation of the impregnated papers of all Examples and Comparative Examples. This quality evaluation test was performed under environmental conditions of temperature 23 ± 2 ° C. and humidity 50 ± 2% in accordance with JIS-P8111.
なお、表３中の「熱可塑性樹脂の含有量対含浸原紙比（％）」とは、塗工液の含浸塗布量を示すもので、含浸原紙に対する熱可塑性樹脂の含有量である。 The “ratio of thermoplastic resin to impregnated base paper (%)” in Table 3 indicates the impregnated coating amount of the coating liquid, and is the content of the thermoplastic resin relative to the impregnated base paper.
「厚さ方向における吸水時の寸法変化率（％）」とは、吸水時のＺ軸方向の寸法安定性を評価したものである。ＪＩＳ−Ａ５９０５（２００３）の繊維板に規定されている方法で、常温水に２４時間浸漬させた際の、吸水前と吸水後の含浸原紙の紙厚から、下記の（数１）によって算出した値である。
（数１）
吸水厚さ膨張率（％）＝（（吸水後の紙厚−吸水前の紙厚）／吸水前の紙厚）×１００
The “dimensional change rate (%) during water absorption in the thickness direction” is an evaluation of the dimensional stability in the Z-axis direction during water absorption. It was calculated by the following (Equation 1) from the paper thickness of the impregnated base paper before and after water absorption when immersed in normal temperature water for 24 hours by the method prescribed in the fiber board of JIS-A5905 (2003). Value.
(Equation 1)
Water absorption thickness expansion rate (%) = ((paper thickness after water absorption−paper thickness before water absorption) / paper thickness before water absorption) × 100
また、「横方向における吸水時の寸法変化率（％）」とは、含浸紙の吸水時のＸ軸方向の寸法安定性を評価したものである。ＪＩＳ−Ａ５９０５（２００３）の繊維板に規定されている上記の「吸水厚さ膨張率」の測定方法を流用し、常温水に２４時間浸漬させた際の、吸水前の含浸原紙の幅と吸水後の含浸紙の幅から、上記（数１）の紙厚を紙幅に置き換えて算出した値である。 Further, the “dimensional change rate (%) during water absorption in the lateral direction” is an evaluation of the dimensional stability in the X-axis direction during water absorption of the impregnated paper. Applying the measurement method of “water absorption thickness expansion coefficient” defined in the fiberboard of JIS-A5905 (2003) and immersing in normal temperature water for 24 hours, the width and water absorption of the impregnated base paper before water absorption This is a value calculated from the width of the subsequent impregnated paper by replacing the paper thickness in (Equation 1) with the paper width.
「耐衝撃性値（ｍｍ）」とは、凹み量を評価したもので、ＪＩＳ−５６００に記載の「塗料一般試験方法」に規定されているデュポン式落球衝撃窪み試験に準じて測定した凹み量（ｍｍ）を測定したものである。なお、測定条件は、落下おもり重量５００ｇ、落下高さ３０ｃｍ、玉半径６．３５ｍｍとした。 “Impact resistance value (mm)” is an evaluation of the amount of dents, and the amount of dents measured according to the DuPont falling ball impact dimple test defined in “General test method for paint” described in JIS-5600. (Mm) is measured. Measurement conditions were a drop weight weight of 500 g, a drop height of 30 cm, and a ball radius of 6.35 mm.
「層間強度（ＭＰａ）」とは、ＪＡＳ合板平面引張試験に準じて測定した剥離時または、破壊時の最大荷重（ＭＰａ）とした。 “Interlaminar strength (MPa)” was defined as the maximum load (MPa) at the time of peeling or breaking measured according to the JAS plywood plane tensile test.
また、「層間剥離強度（ｇ/１５ｍｍ）」とは、９０度剥離試験により層間剥離強度を評価したもので、ＪＩＳ−Ｋ−６８５４−１（１９９９）に記載の「接着剤−剥離接着強さ試験方法」に規定されている９０度剥離試験に準じて測定した剥離強度を測定したものである。なお、測定条件は、試験片幅（幅方向）１５ｍｍ、長さ（流れ）１５０ｍｍ以上、剥離速度１００ｍｍ/分とした。 Further, the “delamination strength (g / 15 mm)” is an evaluation of delamination strength by a 90-degree peel test, and “adhesive-peel adhesion strength” described in JIS-K-6854-1 (1999). The peel strength measured in accordance with the 90-degree peel test specified in “Test Method” is measured. The measurement conditions were a test piece width (width direction) of 15 mm, a length (flow) of 150 mm or more, and a peeling rate of 100 mm / min.
表３から、本発明に係る含浸紙は、脱ホルムアルデヒド化を達成することができ、シックハウス症候群を防止することができると共に、吸水時の寸法安定性に優れるものとすることができ、床材に好適に用いることができることが分かる。さらに、本含浸紙は、ホルムアルデヒドを含有しなくても床材として要求される耐衝撃性、耐キャスター性、層間強度、及び層間剥離強度を満足させることができることが分かる。 From Table 3, the impregnated paper according to the present invention can achieve deformaldehyde formation, can prevent sick house syndrome, and can be excellent in dimensional stability at the time of water absorption. It turns out that it can use suitably. Further, it can be seen that the impregnated paper can satisfy the impact resistance, caster resistance, interlayer strength, and delamination strength required as a flooring material without containing formaldehyde.
Claims (3)
前記含浸原紙には、原料パルプに対して５〜３０質量％の無機填料と、該無機填料に対して０．１〜５質量％のシランカップリング剤とが内添されており、
前記熱可塑性樹脂は、ブタジエン系ラテックス樹脂及び／又はアクリル系ラテックス樹脂であることを特徴とする含浸紙。 An impregnated paper formed by applying or impregnating an impregnated base paper with a coating liquid containing at least a thermoplastic resin,
In the impregnated base paper, 5 to 30% by mass of an inorganic filler with respect to the raw material pulp and 0.1 to 5% by mass of a silane coupling agent with respect to the inorganic filler are internally added.
The impregnated paper, wherein the thermoplastic resin is a butadiene latex resin and / or an acrylic latex resin.
また、前記含浸原紙は、米坪が７０〜６００ｇ／ｍ２で、かつ、密度が０．４〜０．８５ｇ／ｃｍ３であることを特徴とする請求項１に記載の含浸紙。 Applying or impregnating the coating liquid to the impregnated base paper so that the ratio of the thermoplastic resin content to the impregnated base paper is 15 to 60%,
2. The impregnated paper according to claim 1, wherein the impregnated base paper has a weight of 70 to 600 g / m 2 and a density of 0.4 to 0.85 g / cm 3 .
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| JP2009220335A (en) * | 2008-03-14 | 2009-10-01 | Daio Paper Corp | Impregnated paper for flooring material |
| JP2009243029A (en) * | 2008-03-13 | 2009-10-22 | Kohjin Co Ltd | Dressing sheet |
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| JP2009220335A (en) * | 2008-03-14 | 2009-10-01 | Daio Paper Corp | Impregnated paper for flooring material |
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