JP2017119760A - Water-repellent composition and woody board obtained by adding the same - Google Patents

Water-repellent composition and woody board obtained by adding the same Download PDF

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JP2017119760A
JP2017119760A JP2015256552A JP2015256552A JP2017119760A JP 2017119760 A JP2017119760 A JP 2017119760A JP 2015256552 A JP2015256552 A JP 2015256552A JP 2015256552 A JP2015256552 A JP 2015256552A JP 2017119760 A JP2017119760 A JP 2017119760A
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water
repellent composition
petroleum resin
wax
parts
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JP5981016B1 (en
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敏行 奥田
Toshiyuki Okuda
敏行 奥田
啓典 福井
Takanori Fukui
啓典 福井
義高 田口
Yoshitaka Taguchi
義高 田口
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Chukyo Yushi Co Ltd
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Chukyo Yushi Co Ltd
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Priority to JP2015256552A priority Critical patent/JP5981016B1/en
Priority to JP2016569082A priority patent/JP6182742B1/en
Priority to PCT/JP2016/071989 priority patent/WO2017115488A1/en
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Publication of JP5981016B1 publication Critical patent/JP5981016B1/en
Priority to MYPI2016703894A priority patent/MY173733A/en
Priority to NZ725667A priority patent/NZ725667B/en
Priority to KR1020160148629A priority patent/KR101798393B1/en
Publication of JP2017119760A publication Critical patent/JP2017119760A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27MWORKING OF WOOD NOT PROVIDED FOR IN SUBCLASSES B27B - B27L; MANUFACTURE OF SPECIFIC WOODEN ARTICLES
    • B27M3/00Manufacture or reconditioning of specific semi-finished or finished articles
    • B27M3/04Manufacture or reconditioning of specific semi-finished or finished articles of flooring elements, e.g. parqueting blocks
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34Organic impregnating agents
    • B27K3/44Tar; Mineral oil
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52Impregnating agents containing mixtures of inorganic and organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27NMANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08Moulding or pressing
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/18Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00Purpose of the treatment
    • B27K2240/70Hydrophobation treatment

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Forests & Forestry (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Paper (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent composition which suppresses penetration of an organic component contained in a coating agent into a woody board even when the surface of a floor material of a woody board is subjected to wax coating, does not cause adverse effects such as expansion, deformation and discoloration on the woody board, and is excellent in floor wax resistance.SOLUTION: A water-repellent composition that is added to a material and enhances water resistance of the material contains 70-90 wt.% of wax and 30-10 wt.% of a petroleum resin. The petroleum resin is preferably a copolymer of C5 fraction and C9 fraction.SELECTED DRAWING: None

Description

本発明はパーティクルボード、MDF(中密度繊維板)等の木質ボード、その他の建材中に添加してその撥水性を向上させる撥水性組成物の改良に関する。   The present invention relates to an improvement in a water-repellent composition that is added to a wooden board such as particle board, MDF (medium density fiberboard), or other building materials to improve its water repellency.

一般的に、木質ボードにはその耐水性を確保するため撥水性組成物が添加されている。かかる撥水性組成物として、例えば特許文献1や特許文献2にはパラフィンワックス、石油樹脂、アスファルト、シリコーン系樹脂、フッ素系樹脂等が例示されている。中でも、価格の面からパラフィンワックスが選択される場合が多い。   In general, a water repellent composition is added to a wooden board to ensure its water resistance. As such water-repellent compositions, for example, Patent Document 1 and Patent Document 2 illustrate paraffin wax, petroleum resin, asphalt, silicone resin, fluorine resin, and the like. Among them, paraffin wax is often selected from the viewpoint of price.

特公平6−35547号公報Japanese Patent Publication No. 6-35547 特公平8−26305号公報Japanese Patent Publication No. 8-26305

パラフィンワックス等のワックスは優れた撥水性を備えるので、木質ボード中に添加されたときこれに優れた耐水性を与える。
他方、木質ボードが建材、例えば床材に使われたとき、その床材の表面にいわゆるワックスコーティングを施すと、コーティング剤に含まれる有機成分が木質ボードに浸透する。浸透した有機成分は膨張、変形、変色その他の悪影響を木質ボードに生じさせるおそれがある。このとき、ワックスは有機成分と親和性を有するので、木質ボードに対する当該有機成分の浸透を有効に妨げられない。
Since waxes such as paraffin wax have excellent water repellency, they provide excellent water resistance when added to a wooden board.
On the other hand, when a wooden board is used as a building material, for example, a flooring material, when a so-called wax coating is applied to the surface of the flooring material, an organic component contained in the coating agent penetrates into the wooden board. The permeated organic components can cause swelling, deformation, discoloration and other adverse effects on the wooden board. At this time, since the wax has an affinity with the organic component, the penetration of the organic component into the wooden board is not effectively prevented.

本発明者らは、上記の課題を解決すべく鋭意検討を重ねてきた結果、撥水性組成物としてワックスと石油樹脂とを所定の比率で併用すると、撥水性はもとよりフロアワックス剤をはじめとする有機成分に対しても安定することを見出した。
即ち、この発明の第1の局面は次のように規定される。
木質ボード等の素材に添加させる撥水性組成物であって、
ワックスを70〜90重量%、
石油樹脂を30〜10重量%、含んでなる撥水性組成物。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a wax and petroleum resin in a predetermined ratio as a water-repellent composition. It was found that the organic component is stable.
That is, the first aspect of the present invention is defined as follows.
A water repellent composition added to a material such as a wooden board,
70-90% by weight of wax,
A water-repellent composition comprising 30 to 10% by weight of a petroleum resin.

ここに、ワックスにはパラフィンワックスの他に、オレフィンワックスやモンタンワックス、フィッシャートロプッシュワックスなど、撥水性組成物として汎用的なものを使用できる。
石油樹脂とは石油類のスチームクラッキングによりエチレン、プロピレンなどを製造するエチレンプラントから副生する分解油留分に含まれるジオレフィンおよびモノオレフィン類を単離せずに重合したもので、大別して次の3種に分けられる。分解油留分のうちC5留分を原料にしたものを脂肪族系またはC5系石油樹脂、C9留分を原料にしたものを芳香族系またはC9系石油樹脂、両者を原料としたものをC5C9共重合石油樹脂と呼ぶ。
C5系石油樹脂の主成分はイソプレン、ピペリレン、2−メチルブテン−1および2などの共重合体で共役ジオレフィンは環化構造を有することが多い。その軟化点は70〜100℃である。C9系石油樹脂の主成分はスチレン、ビニルトルエン、α−メチルスチレン、インデンの共重合体でその軟化点は80〜150℃である。C5C9共重合石油樹脂は前述C5、C9の共重合物であり、その軟化点は60〜100℃である。
ここに、ワックス及び石油樹脂はともに、従来より、防水性を付与するために木質ボードへ添加させられていた。両者を共用することも特許文献1及び2に示唆されている。より具体的には特許文献1の実施例2においてパラフィンワックス:石油樹脂=96重量部:2重量部の配合例が開示されている。同様に、特許文献2の実施例8においてパラフィンワックス:石油樹脂=96重量部:1重量部の配合例が開示されている。
これに対し、この発明の第1の局面に記載の発明では、ワックスと石油樹脂との配合比を前者:後者=70〜90重量%:30〜10重量%とすることで、フロアワックス剤その他の有機成分に対する耐性の向上を図っている。
Here, in addition to paraffin wax, general-purpose water-repellent compositions such as olefin wax, montan wax, and Fischer-Tropsch wax can be used as the wax.
Petroleum resins are polymerized without isolating diolefins and monoolefins contained in cracked oil fractions by-produced from ethylene plants that produce ethylene, propylene, etc. by steam cracking of petroleum. There are three types. Among the cracked oil fractions, aliphatic or C5 petroleum resins made from C5 fraction as raw materials, aromatic or C9 petroleum resins made from C9 fractions as raw materials, and C5C9 produced from both as raw materials Called copolymerized petroleum resin.
The main component of the C5 petroleum resin is a copolymer such as isoprene, piperylene, 2-methylbutene-1 and 2, and the conjugated diolefin often has a cyclized structure. Its softening point is 70-100 ° C. The main component of the C9 petroleum resin is a copolymer of styrene, vinyltoluene, α-methylstyrene, and indene, and its softening point is 80 to 150 ° C. C5C9 copolymer petroleum resin is a copolymer of the aforementioned C5 and C9, and its softening point is 60 to 100 ° C.
Here, both wax and petroleum resin have been conventionally added to a wooden board in order to impart waterproofness. It is also suggested in Patent Documents 1 and 2 that both are shared. More specifically, in Example 2 of Patent Document 1, a blending example of paraffin wax: petroleum resin = 96 parts by weight: 2 parts by weight is disclosed. Similarly, in Example 8 of Patent Document 2, a blending example of paraffin wax: petroleum resin = 96 parts by weight: 1 part by weight is disclosed.
On the other hand, in the invention described in the first aspect of the present invention, the ratio of the wax and the petroleum resin is the former: the latter = 70 to 90% by weight: 30 to 10% by weight. To improve resistance to organic components.

ワックスと石油樹脂とは、相互に溶融可能な場合は、溶融後に当該溶融物を分散質として水(分散媒)に分散させて水系エマルジョンとすることができる。石油樹脂としてC9系を採用した場合にはワックスと溶融させることができないので、この場合はワックスと石油樹脂とをそれぞれエマルジョン化し、その後両者を混合する。勿論、相互に溶融可能なワックスと石油樹脂とを個別にエマルジョン化し、これらを混合してもよい。
エマルジョンを作成する際に使用する界面活性剤には、アニオン性、カチオン性、ノニオン性または両性の界面活性剤、水溶性高分子化合物等を用いることができ、これらは単独ないしは数種類を組み合わせて用いることができる。次にそれらの例を示すが、その他の成分はこれに限定されるものではない。
アニオン性界面活性剤としては、脂肪酸塩、ポリオキシエチレンアルキルエーテルカルボン酸塩、ジアルキルスルホコハク酸塩、アルキルベンゼンスルホン酸塩、アルキルエーテル硫酸エステル塩、アルキルリン酸エステル塩等が挙げられる。
カチオン性界面活性剤としては、アルキルアミン塩、第4級アンモニウム塩、アルキルピリジニウム塩等が挙げられる。
ノニオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンソルビタン脂肪酸部分エステル、脂肪酸ジエタノールアミド等が挙げられる。
両性界面活性剤としては、アルキルベタイン、アルキルアミンオキサイド等が挙げられる。
水溶性高分子化合物としては、メチルセルロース、カルボキシルメチルセルロース、化工デンプン、アラビアガム、ポリビニルアルコール、ポリアクリル酸塩、スチレン−無水マレイン酸共重合体塩、ポリエチレングリコール等が挙げられる。
本発明におけるエマルジョンは、ワックス又は石油樹脂に加えて、それらを溶媒に分散又は溶解させるために必要なその他の成分を含有することができる。
When the wax and the petroleum resin can be melted with each other, the melt can be dispersed in water (dispersion medium) as a dispersoid after melting to form an aqueous emulsion. When the C9 system is used as the petroleum resin, it cannot be melted with the wax. In this case, the wax and the petroleum resin are emulsified, and then both are mixed. Of course, the mutually meltable wax and petroleum resin may be separately emulsified and mixed.
As the surfactant used in preparing the emulsion, an anionic, cationic, nonionic or amphoteric surfactant, a water-soluble polymer compound, or the like can be used, and these are used alone or in combination of several kinds. be able to. Examples thereof are shown below, but the other components are not limited thereto.
Examples of the anionic surfactant include fatty acid salts, polyoxyethylene alkyl ether carboxylates, dialkyl sulfosuccinates, alkyl benzene sulfonates, alkyl ether sulfate esters, and alkyl phosphate ester salts.
Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, and alkylpyridinium salts.
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid partial ester, fatty acid diethanolamide, and the like.
Examples of amphoteric surfactants include alkylbetaines and alkylamine oxides.
Examples of the water-soluble polymer compound include methyl cellulose, carboxymethyl cellulose, modified starch, gum arabic, polyvinyl alcohol, polyacrylate, styrene-maleic anhydride copolymer salt, polyethylene glycol and the like.
In addition to waxes or petroleum resins, the emulsions in the present invention may contain other components necessary to disperse or dissolve them in a solvent.

以下、第1の局面に記載の発明の効果を確認する実施例及び比較例の説明を行う。
なお、この明細書において、特に断りの無い限り、「部」は重量部を指し、「%」は重量%を指す。
(実施例1)
<撥水性組成物の調製>
融点56℃のパラフィンワックス90部と軟化点98℃のC5系石油樹脂10部を加熱し溶融した。界面活性剤として、スチレン−無水マレイン酸共重合体のカリウム塩7.2部と部分けん化PVA0.8部、水162部を混合し90℃に加熱した溶液中に、ワックス/樹脂溶融物を撹拌しながら添加し乳化した。ホモジナイザーにて微細化した後冷却し、1.5μmの40%品エマルジョン(実施例1の撥水性組成物)を得た。
Hereinafter, examples and comparative examples for confirming the effects of the invention described in the first aspect will be described.
In this specification, “parts” refers to parts by weight and “%” refers to weight percent unless otherwise specified.
Example 1
<Preparation of water repellent composition>
90 parts of paraffin wax having a melting point of 56 ° C. and 10 parts of C5 petroleum resin having a softening point of 98 ° C. were heated and melted. As a surfactant, 7.2 parts of potassium salt of styrene-maleic anhydride copolymer, 0.8 parts of partially saponified PVA, and 162 parts of water were mixed and heated to 90 ° C., and the wax / resin melt was stirred. The mixture was added and emulsified. The mixture was refined by a homogenizer and then cooled to obtain a 40% product emulsion (water repellent composition of Example 1) of 1.5 μm.

<MDFの作成>
木質ボードとしてMDFを調製する例を示す。
含水率5%に乾燥した木質ファイバーに対して、上記で得た撥水性組成物を固形分比で0.7%、ポリメリックMDI(東ソー製ミリオネートMR−200)を固形分比で7%となるように、ブレンダーにて撹拌しながらそれぞれスプレー塗布した。さらに気流下での撹拌乾燥を行い含水率15%の木質ファイバー混合物を得た。
<熱プレス成形>
予め、ステンレス製成形板の表面に離型剤(中京油脂製リケイ剤R−599)を塗布したステンレス製成形板の上に40cm角の木枠を置き、木枠内に上記で得た木質ファイバー混合物を均一に乗せフォーミングした。木枠を取り除いた後、この成形板に離型剤を処理したもう一枚のステンレス製成形板を載せ、プレス温度180℃のホットプレス装置により、25kgf/cm2にて、厚さ3mmとなるように1分間熱圧して成形した。成形後、サンダーにて表面より0.2mmを研磨し、MDFを得た。
<MDF creation>
The example which prepares MDF as a wooden board is shown.
With respect to the wood fiber dried to a moisture content of 5%, the water repellent composition obtained above has a solid content ratio of 0.7%, and Polymeric MDI (Tosoh Millionate MR-200) has a solid content ratio of 7%. As described above, each was applied by spraying while stirring with a blender. Further, the mixture was stirred and dried under an air stream to obtain a wood fiber mixture having a water content of 15%.
<Hot press molding>
A 40 cm square wooden frame is placed on a stainless steel molding plate that has been previously coated with a release agent (Ricoh R-599 made of Chukyo Yushi) on the surface of the stainless steel molding plate, and the wood fiber obtained above is placed inside the wooden frame. The mixture was uniformly placed and formed. After removing the wooden frame, another stainless steel molding plate treated with a release agent is placed on this molding plate, and the thickness is set to 3 mm at 25 kgf / cm 2 with a hot press apparatus at a press temperature of 180 ° C. And then molded by hot pressing for 1 minute. After molding, 0.2 mm from the surface was polished with a sander to obtain MDF.

(実施例2〜3)
実施例2の撥水性組成物は、実施例1において、撥水性組成物としてパラフィンワックスを80部としてC5系石油樹脂20部としたものである。
実施例3の撥水性組成物は、実施例1において、撥水性組成物としてパラフィンワックスを70部としてC5系石油樹脂30部としたものである。
(Examples 2-3)
The water repellent composition of Example 2 is the same as Example 1 except that 80 parts of paraffin wax is used as the water repellent composition and 20 parts of C5 petroleum resin is used.
The water repellent composition of Example 3 is the same as that of Example 1 except that the water repellent composition is 70 parts paraffin wax and 30 parts C5 petroleum resin.

(比較例1〜3)
比較例1の撥水性組成物は、実施例1において、撥水性組成物としてパラフィンワックスを100部としてC5系石油樹脂を用いないものである。
比較例2の撥水性組成物は、実施例1において、撥水性組成物としてパラフィンワックスを95部としてC5系石油樹脂5部としたものである。
比較例3の撥水性組成物は、実施例1において、撥水性組成物としてパラフィンワックスを60部としてC5系石油樹脂40部としたものである。
(比較例4)
比較例4の撥水性組成物は、実施例1において、出願人である中京油脂株式会社が販売する商品名(セロゾールR−170)を撥水性組成物として用いたものである。
(Comparative Examples 1-3)
The water repellent composition of Comparative Example 1 is the same as that of Example 1 except that 100 parts of paraffin wax is used as the water repellent composition and no C5 petroleum resin is used.
The water-repellent composition of Comparative Example 2 is the same as Example 1 except that 95 parts of paraffin wax is used as the water-repellent composition to make 5 parts of C5 petroleum resin.
The water-repellent composition of Comparative Example 3 is the same as Example 1 except that 60 parts of paraffin wax is used as the water-repellent composition and 40 parts of C5 petroleum resin is used.
(Comparative Example 4)
The water-repellent composition of Comparative Example 4 uses the product name (Cerosol R-170) sold by the applicant, Chukyo Oil & Fat Co., Ltd. as the water-repellent composition in Example 1.

<耐フロアワックス性の評価>
各実施例及び比較例で得られたMDFを5cm角に切断し試験片とした。重量と外寸から密度を算出した後、試験片の両面にOPPテープ(積水化学製オリエンテープNo.830)を貼付し、フロアワックス(リンレイ製オール)中に切断部から3cmの高さまで浸漬した。5分後に取り出し、高さ1.5cmの位置での両端部の厚さ膨張率、高さ1.5cmの位置での端部から中心部への浸透による膨らみを示す距離を測定し浸透距離とした。得られた結果を表1に示す。

Figure 2017119760
<Evaluation of floor wax resistance>
The MDF obtained in each Example and Comparative Example was cut into 5 cm squares to obtain test pieces. After calculating the density from the weight and outer dimensions, an OPP tape (Orient tape No. 830 manufactured by Sekisui Chemical Co., Ltd.) was applied to both sides of the test piece, and immersed in floor wax (all made by Linley) to a height of 3 cm from the cut portion. . Take out after 5 minutes, measure the thickness expansion rate of both ends at a position of 1.5 cm in height, and measure the distance indicating the swelling due to the penetration from the end to the center at a position of 1.5 cm in height. did. The obtained results are shown in Table 1.

Figure 2017119760

表1の結果から、実施例の撥水性組成物を添加させた木質ボードは耐フロアワックス性に優れ、出願人である中京油脂株式会社が販売中の撥水性組成物よりその特性が優れている。
また、比較例2及び比較例3の結果より、ワックスと石油樹脂との配合比は前者:後者=90〜70重量%:10〜30重量%が好ましいことがわかる。
更に好ましくは、前者:後者=84〜76重量%:16〜24重量%である。
From the results shown in Table 1, the wood board to which the water-repellent compositions of the examples were added has excellent floor wax resistance, and the characteristics are superior to the water-repellent compositions currently sold by the applicant, Chukyo Yushi Co., Ltd. .
From the results of Comparative Example 2 and Comparative Example 3, it can be seen that the blending ratio of wax and petroleum resin is preferably the former: latter = 90 to 70% by weight: 10 to 30% by weight.
More preferably, the former: latter = 84 to 76% by weight: 16 to 24% by weight.

(実施例4−7)
実施例4の撥水性組成物は、実施例2において、石油樹脂としてC5C9系石油樹脂(C5比率70%、軟化点72℃)を用いたものである。
実施例5の撥水性組成物は、実施例2において、石油樹脂としてC5C9系石油樹脂(C5比率60%、軟化点96℃)を用いたものである。
実施例6の撥水性組成物は、実施例2において、石油樹脂としてC5C9系石油樹脂(C5比率50%、軟化点70℃)を用いたものである。
実施例7の撥水性組成物は、実施例2において、石油樹脂としてC5C9系石油樹脂(C5比率30%、軟化点95℃)を用いたものである。
これら実施例4−7の撥水性組成物についても実施例1−3と同様にして耐フロアワワックス性を試験した。結果を表2に示す。

Figure 2017119760
表2の結果より、石油樹脂としてC5C9系の共重合体樹脂を用いると、耐フロアワックス性が更に向上することがわかる。C5C9系石油樹脂の中でもC5比率を比較的小さくすることが好ましく、その見地からC5比率は65〜20%とすることができる。更に好ましくは、C5比率を34〜26%とする。 (Example 4-7)
The water-repellent composition of Example 4 uses C5C9 petroleum resin (C5 ratio 70%, softening point 72 ° C.) as the petroleum resin in Example 2.
The water-repellent composition of Example 5 uses C5C9 petroleum resin (C5 ratio 60%, softening point 96 ° C.) as the petroleum resin in Example 2.
The water-repellent composition of Example 6 is obtained by using C5C9 petroleum resin (C5 ratio 50%, softening point 70 ° C.) as the petroleum resin in Example 2.
The water-repellent composition of Example 7 uses C5C9 petroleum resin (C5 ratio 30%, softening point 95 ° C.) as the petroleum resin in Example 2.
These water repellent compositions of Example 4-7 were also tested for floor wax resistance in the same manner as in Example 1-3. The results are shown in Table 2.
Figure 2017119760
From the results in Table 2, it can be seen that the floor wax resistance is further improved when a C5C9 copolymer resin is used as the petroleum resin. Among the C5C9 petroleum resins, it is preferable to make the C5 ratio relatively small, and from this viewpoint, the C5 ratio can be set to 65 to 20%. More preferably, the C5 ratio is 34 to 26%.

以下、C9系石油樹脂について検討する。C9系石油樹脂はワックスと溶融しないので、実施例8では次のようにして撥水組成物を調製した。
<実施例8の撥水性組成物の調製方法>
融点56℃のパラフィンワックス100部を加熱し溶融した。ステアリン酸カリウム塩5.0部と部分けん化PVA0.6部、水162部を混合し90℃に加熱した溶液中に、ワックス溶融物を撹拌しながら添加し乳化した。ホモジナイザーにて微細化した後冷却し、1.5μmの40%品エマルジョンを得た。軟化点94℃のC9系石油樹脂100部をトルエン100部に溶解した。スチレン−無水マレイン酸共重合体のアンモニウム塩12部、水45部の水溶液中に、樹脂溶液を撹拌しながら添加し乳化した。ホモジナイザーにて微細化した後、水123部を加え、減圧にてトルエンを除去し、1.0μmの40%品エマルジョンを得た。得られたワックスエマルジョンと樹脂エマルジョンを、ワックス/樹脂比率が80/20となる様に混合し、実施例8の撥水性組成物とした。
Hereinafter, C9 petroleum resin will be examined. Since C9 petroleum resin does not melt with wax, in Example 8, a water repellent composition was prepared as follows.
<Method for Preparing Water-Repellent Composition of Example 8>
100 parts of paraffin wax having a melting point of 56 ° C. was heated and melted. A wax melt was added to a solution prepared by mixing 5.0 parts of potassium stearate salt, 0.6 parts of partially saponified PVA, and 162 parts of water and heated to 90 ° C. while stirring, and emulsified. The mixture was refined with a homogenizer and then cooled to obtain a 40% product emulsion of 1.5 μm. 100 parts of a C9 petroleum resin having a softening point of 94 ° C. was dissolved in 100 parts of toluene. The resin solution was added and emulsified in an aqueous solution of 12 parts of an ammonium salt of a styrene-maleic anhydride copolymer and 45 parts of water while stirring. After refining with a homogenizer, 123 parts of water was added, and toluene was removed under reduced pressure to obtain a 40% product emulsion of 1.0 μm. The obtained wax emulsion and resin emulsion were mixed so that the wax / resin ratio would be 80/20, whereby the water repellent composition of Example 8 was obtained.

(実施例9〜12)
実施例9の撥水性組成物は、実施例8において、石油樹脂としてC5C9系石油樹脂(C5比率70%)を用いたものである。
実施例10の撥水性組成物は、実施例8において、石油樹脂としてC5C9系石油樹脂(C5比率60%)を用いたものである。
実施例11の撥水性組成物は、実施例8において、石油樹脂としてC5C9系石油樹脂(C5比率50%)を用いたものである。
実施例12の撥水性組成物は、実施例8において、石油樹脂としてC5C9系石油樹脂(C5比率30%)を用いたものである。
(比較例5−6)
比較例5の撥水性組成物は、実施例2において石油樹脂を、軟化点84℃のロジン変性グリセリンエステルに変えたものである。
比較例6の撥水性組成物は、実施例8において石油樹脂をガラス転移点48℃のメタクリル酸イソブチル樹脂に変えたものである。
これら実施例8−12の撥水性組成物、及び比較例5−6についても実施例1−3と同様にして耐フロアワックス性を試験した。結果を表3に示す。

Figure 2017119760
表3の結果より、C9系石油樹脂もワックスと所定割合で共用されることで優れた耐フロアワックス性を発揮する。
また、撥水性組成物を構成するワックス成分と石油樹脂成分とは、それらを溶融可能であれば、溶融後にエマルジョン化してもまたそれぞれ独立してエマルジョン化しても、同等の耐フロアワックス性能を有することがわかる。 (Examples 9 to 12)
The water-repellent composition of Example 9 is obtained by using C5C9 petroleum resin (C5 ratio 70%) as the petroleum resin in Example 8.
The water-repellent composition of Example 10 is obtained by using C5C9 petroleum resin (C5 ratio 60%) as the petroleum resin in Example 8.
The water-repellent composition of Example 11 is obtained by using C5C9 petroleum resin (C5 ratio 50%) as the petroleum resin in Example 8.
The water-repellent composition of Example 12 is obtained by using C5C9 petroleum resin (C5 ratio 30%) as the petroleum resin in Example 8.
(Comparative Example 5-6)
The water-repellent composition of Comparative Example 5 is obtained by replacing the petroleum resin in Example 2 with a rosin-modified glycerin ester having a softening point of 84 ° C.
The water-repellent composition of Comparative Example 6 was obtained by replacing the petroleum resin in Example 8 with an isobutyl methacrylate resin having a glass transition point of 48 ° C.
These water repellent compositions of Examples 8-12 and Comparative Example 5-6 were also tested for floor wax resistance in the same manner as in Example 1-3. The results are shown in Table 3.

Figure 2017119760
From the results shown in Table 3, C9 petroleum resin also exhibits excellent floor wax resistance when used in a predetermined ratio with wax.
In addition, the wax component and petroleum resin component constituting the water-repellent composition have the same floor wax resistance if they can be melted, whether they are emulsified after melting or emulsified independently. I understand that.

この発明は、上記発明の実施形態の説明に何ら限定されるものではない。特許請求の範囲の記載を逸脱せず、当業者が容易に想到できる範囲で種々の変形態様もこの発明に含まれる。
上記の例では、この撥水性組成物はもっぱら木質ボードに用いられたが、その他にも、紙、繊維、セメント、土壌改良材等の素材に適用可能である。
撥水性組成物を構成するワックス、石油樹脂及び界面活性剤の選択、更には木質ボード等適用される素材に対する添加量は、適用される素材の用途等に応じて任意に選択される。
The present invention is not limited to the description of the embodiment of the invention. Various modifications may be included in the present invention as long as those skilled in the art can easily conceive without departing from the description of the scope of claims.
In the above example, this water-repellent composition was used exclusively for wood boards, but can be applied to other materials such as paper, fiber, cement, and soil conditioner.
Selection of the wax, petroleum resin and surfactant constituting the water-repellent composition, and the amount added to the applied material such as a wooden board is arbitrarily selected according to the application of the applied material.

Claims (5)

素材に添加されて該素材の耐水性を向上させる撥水性組成物であって、
ワックスを70〜90重量%、
石油樹脂を30〜10重量%、含んでなる撥水性組成物。
A water repellent composition that is added to a material to improve the water resistance of the material,
70-90% by weight of wax,
A water-repellent composition comprising 30 to 10% by weight of a petroleum resin.
前記石油樹脂はC5留分とC9留分の共重合体である、請求項1に記載の撥水性組成物。   The water repellent composition according to claim 1, wherein the petroleum resin is a copolymer of a C5 fraction and a C9 fraction. 前記共重合体は前記C5留分を65〜20重量%、C9留分を35〜80重量%とする、請求項2に記載の撥水性組成物。   The water-repellent composition according to claim 2, wherein the copolymer contains 65 to 20% by weight of the C5 fraction and 35 to 80% by weight of the C9 fraction. 前記ワックスと石油樹脂とは溶融されて分散質となり、
分散媒として水を採用したエマルジョンからなる、請求項3に記載の撥水性組成物。
The wax and petroleum resin are melted to become a dispersoid,
The water-repellent composition according to claim 3, comprising an emulsion employing water as a dispersion medium.
請求項1〜4の何れかに記載の撥水性組成物が添加されている木質ボード。   A wooden board to which the water-repellent composition according to any one of claims 1 to 4 is added.
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