JP4332578B1 - Modifier for imparting self-extinguishing properties to organic polymer products, method of use thereof, and organic polymer products having self-extinguishing properties - Google Patents
Modifier for imparting self-extinguishing properties to organic polymer products, method of use thereof, and organic polymer products having self-extinguishing properties Download PDFInfo
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- JP4332578B1 JP4332578B1 JP2008070278A JP2008070278A JP4332578B1 JP 4332578 B1 JP4332578 B1 JP 4332578B1 JP 2008070278 A JP2008070278 A JP 2008070278A JP 2008070278 A JP2008070278 A JP 2008070278A JP 4332578 B1 JP4332578 B1 JP 4332578B1
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Abstract
【課題】物性を低下させることなく、有機高分子製品に対して簡易且つ低コストで自己消火性を付与することができ、有害ガスが発生の原因とならない、有機高分子製品の改質剤、その使用方法、およびその製品の提供。
【解決手段】吸水性ポリマーの存在下でケイ素アルコキシドを加水分解重縮合したシロキサン化合物を含む溶液であって、該シロキサン化合物が、その２９Si-NMR測定スペクトルの帰属において、Qｎ（ｎ＝０〜４）構造を示すシグナルにおけるQ４構造を示すシグナルの面積と、Q１、Q２、Q３構造を示すシグナルの面積の和との比SQ４/（SQ１＋SQ２＋SQ３）が１．２０以下である有機高分子製品に自己消火性を付与する改質剤。
ここでQｎ構造とは、シリカの構成単位であるSiO4四面体単位の酸素原子のうちの架橋酸素原子（2つのSiと結合している酸素原子）の数に応じて決まる化学的構造をいい、QnのnはSiO４単位の結合度であり、架橋酸素原子の数である。
【選択図】なしAn organic polymer product modifier capable of imparting self-extinguishing properties to organic polymer products easily and at low cost without deteriorating physical properties, and causing no generation of harmful gases, How to use it and provide its products.
A solution containing a siloxane compound obtained by hydrolytic polycondensation of silicon alkoxide in the presence of a water-absorbing polymer, wherein the siloxane compound has Q n (n = 0) in the assignment of its 29 Si-NMR measurement spectrum. 4) Ratio S Q4 / (S Q1 + S Q2 + S Q3 ) of the signal area indicating the Q 4 structure and the sum of the signal areas indicating the Q 1 , Q 2 , and Q 3 structures in the signal indicating the structure is 1 A modifier that imparts self-extinguishing properties to organic polymer products that are 20 or less.
Here, Q n structure, the chemical structure depends on the number of bridging oxygen atoms of the oxygen atom of the SiO 4 tetrahedral units is a structural unit of the silica (oxygen atom bonded to two Si) Good, n in Qn is the degree of bonding of SiO 4 units and the number of bridging oxygen atoms.
[Selection figure] None
Description
本発明は、有機高分子製品に自己消火性を付与する改質剤、その使用方法、および得られた自己消火性を有する有機高分子製品に関する。 The present invention relates to a modifier imparting self-extinguishing properties to an organic polymer product, a method of using the same, and the obtained organic polymer product having self-extinguishing properties.
従来からプラスチック、ゴム、木材、紙などの有機高分子は、優れた力学的性質、熱的性質を持つため幅広い用途分野に用いられている。
通常、これらの有機高分子は極めて燃えやすいため、自己消火性が要求される分野で用いるためには、ハロゲン化合物系難燃剤を添加することが一般的に行われている。しかしながら、火災時に、ハロゲン化合物系難燃剤を添加している有機高分子が有害なガスを発生するという問題が生じたため、近年では著しく使用が制限されている。したがって、ハロゲン化合物系難燃剤の代わりにリン系、ホウ素系難燃材を有機高分子に添加することが行われるようになったが、リン系、ホウ素系難燃材によって要求される自己消火性を達成するためには大量のリン系、ホウ素系難燃材を添加しなければならない。そのため、物性が低下しコストが上昇するために応用分野が限定されている。
一方で、木材を難燃化させるために、次に例示するような種々の製造方法が実施されている。
Conventionally, organic polymers such as plastic, rubber, wood, and paper have been used in a wide range of application fields because of their excellent mechanical and thermal properties.
Usually, since these organic polymers are extremely flammable, a halogen compound-based flame retardant is generally added for use in fields where self-extinguishing properties are required. However, the use of a halogen compound-based flame retardant in an organic polymer during a fire has caused a problem of generating harmful gases, so that its use has been remarkably restricted in recent years. Therefore, phosphorous and boron flame retardants have been added to organic polymers instead of halogenated flame retardants, but the self-extinguishing properties required by phosphorous and boron flame retardants In order to achieve this, a large amount of phosphorus-based and boron-based flame retardants must be added. Therefore, the application field is limited because the physical properties decrease and the cost increases.
On the other hand, in order to make wood flame-retardant, various production methods as exemplified below are implemented.
例えば、難燃化した木材を簡単な方法で大量生産することを目的とした改質木材の製造方法が提案されている。より具体的には、木材の中に一種或いは二種以上の金属アルコキシドの溶液を含浸させ、その後この金属アルコキシドを加水分解もしくは加熱分解させることによって、これを不燃性の金属酸化物に変え、これによって木材を難燃化木材に改質する方法が開示されている（特許文献１参照）。 For example, a method for producing modified wood intended to mass-produce flame-retardant wood by a simple method has been proposed. More specifically, by impregnating wood with a solution of one or more metal alkoxides, and then hydrolyzing or thermally decomposing the metal alkoxide, this is converted into a nonflammable metal oxide. Discloses a method for modifying wood into flame-retardant wood (see Patent Document 1).
また、高い難燃性と耐熱性を木材に付与することができる難燃性・耐熱性木材の製造方法を提供することを目的とした難燃性・耐熱性木材の製造方法が提案されている。より具体的には、ケイ素アルコキシド、ホウ素アルコキシドおよびリンアルコキシドから選ばれる少なくとも１種の金属アルコキシドに、アルカリ金属化合物または/およびアルカリ土類金属化合物を添加した溶液を木材中に含浸させ、木材細胞空隙内で、これらを加水分解または加熱分解し、次いで重縮合させて不燃性の金属酸化物を生成させることによって、木材に高い難燃性と耐熱性とを付与することができる（特許文献２参照）。 Also, a method for producing flame retardant and heat resistant wood has been proposed for the purpose of providing a method for producing flame retardant and heat resistant wood that can impart high flame resistance and heat resistance to wood. . More specifically, at least one metal alkoxide selected from silicon alkoxide, boron alkoxide and phosphorus alkoxide is impregnated in wood with a solution obtained by adding an alkali metal compound or / and an alkaline earth metal compound, and wood cell voids are obtained. In the above, these are hydrolyzed or thermally decomposed, and then polycondensed to produce a non-combustible metal oxide, whereby high flame retardancy and heat resistance can be imparted to wood (see Patent Document 2). ).
また、発明者は、木材の持つ雨水などの水に晒されると劣化する欠点を改良し、しかも木材の長所である特有の外観および調湿性をできるだけ保持できる木材の表面改良剤として、吸水性ポリマーおよび／または無機微粒子の存在下で金属アルコキシドを加水分解重縮合した反応物からなる、調湿性表面に適用してその調湿性を維持しつつ水の浸透性を著しく小さくする木材の表面改質剤を提言した（特許文献３参照）。 In addition, the inventor has improved the defect that deteriorates when exposed to water, such as rain water, and has a water-absorbing polymer as a surface improvement agent for wood that can retain the unique appearance and humidity control properties of wood as much as possible. And / or a wood surface modifier comprising a reaction product obtained by hydrolytic polycondensation of a metal alkoxide in the presence of inorganic fine particles, which is applied to a humidity control surface and maintains its humidity control property while significantly reducing water permeability. (Refer to Patent Document 3).
しかしながら、特許文献１に記載の改質木材の製造方法においては、木材を難燃化するために、１０〜４５％という多量の金属酸化物が形成されるため、重量が著しく増加するという課題があった。また、木材中で化学反応を行うために、木材を収納する大きな反応容器が必要であり、また反応効率も低下するので、経済的制約が大きくなるという課題があることからも、実用化に限界があった。 However, in the method for producing the modified wood described in Patent Document 1, a large amount of metal oxide of 10 to 45% is formed in order to make the wood flame-retardant, so that there is a problem that the weight is remarkably increased. there were. In addition, in order to perform chemical reactions in wood, a large reaction container for storing wood is necessary, and the reaction efficiency also decreases, so there is a problem that economic constraints become large, so there is a limit to practical application. was there.
特許文献２に記載の難燃性・耐熱性木材の製造方法においても、SiO２、B２O３、Na２Oなどの金属酸化物が９〜３６％と多量に形成されるため、重量が著しく増加しやすいという課題があった。また、特許文献１と同様に、木材中で化学反応を行うために経済的制約が大きくなるという課題があった。 Also in the method for producing flame-retardant and heat-resistant wood described in Patent Document 2, metal oxides such as SiO 2 , B 2 O 3 , Na 2 O and the like are formed in a large amount of 9 to 36%. There was a problem that it increased remarkably. In addition, similar to Patent Document 1, there is a problem that economic restrictions increase because chemical reactions are performed in wood.
特許文献３に記載の表面改質剤は、調湿性表面に適用してその調湿性を維持しつつ水の浸透性を著しく小さくする表面改質剤であって、難燃化する改質剤を目的とするものではない。 The surface modifier described in Patent Document 3 is a surface modifier that is applied to a humidity-controlling surface to significantly reduce the water permeability while maintaining the humidity-controlling property. It is not intended.
シリカ粒子は無機酸化物であり、それ自身燃えない。しかし、シリカには炭化皮膜形成能力がないために有機高分子製品に自己消火性を付与するためには、多量のシリカが必要となる。そのため、重量が著しく増加し、また透明プラスチック製品の場合、透明性が損なわれるという問題が生じる。 Silica particles are inorganic oxides and do not burn themselves. However, since silica does not have the ability to form a carbonized film, a large amount of silica is required to impart self-extinguishing properties to organic polymer products. Therefore, the weight increases remarkably, and in the case of a transparent plastic product, there arises a problem that transparency is impaired.
本発明は、物性を低下させることなく、有機高分子製品に対して簡易且つ低コストで自己消火性を付与することができ、有害ガスが発生の原因とならない、有機高分子製品の改質剤、その使用方法、および自己消火性を有する有機高分子製品を提供することを目的とする。 The present invention can provide a self-extinguishing property to an organic polymer product easily and at low cost without deteriorating physical properties, and does not cause generation of harmful gas. It is an object to provide a method for using the same, and an organic polymer product having self-extinguishing properties.
第１の発明は、吸水性ポリマーの存在下で下記一般式（１）
［化１］
Si（OR） 4 （１）
（式（１）中、Rは炭素数１〜４のアルキル基を表す。）
で表されるケイ素アルコキシドを加水分解重縮合したシロキサン化合物を含む溶液であって、該シロキサン化合物が、その２９Si-NMR測定スペクトルの帰属において、Qｎ（ｎ＝０〜４）構造を示すシグナルにおけるQ４構造を示すシグナルの面積と、Q１、Q２、Q３構造を示すシグナルの面積の和との比SQ４/（SQ１＋SQ２＋SQ３）が０．２以上０．９０以下であることを特徴とするコーティング、塗布、含浸または加圧注入することにより木材またはダンボール製品に自己消火性を付与する改質剤。
ここでQｎ構造とは、シリカの構成単位であるSiO4四面体単位の酸素原子のうちの架橋酸素原子（2つのSiと結合している酸素原子）の数に応じて決まる化学的構造をいい、QnのnはSiO４単位の結合度であり、架橋酸素原子の数である。
The first invention is the following general formula (1) in the presence of a water-absorbing polymer.
[Chemical 1]
Si (OR) 4 (1)
(In formula (1), R represents an alkyl group having 1 to 4 carbon atoms.)
A signal containing a siloxane compound obtained by hydrolytic polycondensation of a silicon alkoxide represented by the formula: wherein the siloxane compound has a Q n (n = 0 to 4) structure in the assignment of its 29 Si-NMR measurement spectrum. The ratio S Q4 / (S Q1 + S Q2 + S Q3 ) of the signal area showing the Q 4 structure and the sum of the signal areas showing the Q 1 , Q 2 , and Q 3 structures is 0.2 or more and 0.90 or less A modifier that imparts self-extinguishing properties to wood or cardboard products by coating, applying, impregnating or pressure injecting .
Here, Q n structure, the chemical structure depends on the number of bridging oxygen atoms of the oxygen atom of the SiO 4 tetrahedral units is a structural unit of the silica (oxygen atom bonded to two Si) Good, n in Qn is the degree of bonding of SiO 4 units and the number of bridging oxygen atoms.
第２の発明は、第１の発明において、前記吸水性ポリマーがポリアクリル酸金属塩部分架橋体を主体とするポリアクリル酸系吸水性ポリマーであることを特徴とする。 A second invention is characterized in that, in the first invention, the water-absorbing polymer is a polyacrylic acid-based water-absorbing polymer mainly comprising a polyacrylic acid metal salt partially crosslinked product.
第３の発明は、第１または２の発明において、前記吸水性ポリマーの存在下で前記ケイ素アルコキシドを加水分解重縮合させる際に、さらに無機微粒子を共存させることを特徴とする。 A third invention is characterized in that, in the first or second invention, when the silicon alkoxide is hydrolytically polycondensed in the presence of the water-absorbing polymer, inorganic fine particles are further allowed to coexist.
第４の発明は、第１ないし３のいずれかの発明において、前記吸水性ポリマーの存在下で前記ケイ素アルコキシドを加水分解重縮合させる際に、さらにシリコーンオイルまたはシリコーン界面活性剤を共存させることを特徴とする。 According to a fourth invention, in any one of the first to third inventions, when hydrolytic polycondensation of the silicon alkoxide in the presence of the water-absorbing polymer, a silicone oil or a silicone surfactant is further allowed to coexist. Features.
第５の発明は、改質剤として第１ないし４のいずれかの発明に係る改質剤を木材、ダンボールまたはプラスチック製品にコーティング、塗布、含浸または加圧注入することにより適用することを特徴とする木材、ダンボールまたはプラスチック製品に自己消火性を付与する方法である。
A fifth invention is characterized in that the modifier according to any one of the first to fourth inventions is applied as a modifier by coating, applying, impregnating or pressurizing the wood, cardboard or plastic product. It is a method to give self-extinguishing properties to wood, cardboard or plastic products.
第６の発明は、第５の発明において、前記シロキサン化合物を前記木材、ダンボールまたはプラスチックに０．０１〜５．０重量%含有させることを特徴とする。
A sixth invention is characterized in that, in the fifth invention, 0.01 to 5.0% by weight of the siloxane compound is contained in the wood, cardboard or plastic .
第７の発明は、第５または６に係る木材、ダンボールまたはプラスチック製品に自己消火性を付与する方法を用いて得られることを特徴とする自己消火性を有する木材、ダンボールまたはプラスチック製品である。
A seventh aspect of the invention, wood having self-extinguishing properties, characterized in that it is obtained by using a method for imparting self-extinguishing properties to wood, cardboard or plastic product according to the fifth or 6, a cardboard or plastic products.
本発明によれば、有機高分子製品固有の物性を低下させることなく、有機高分子製品に対して簡易且つ低コストで自己消火性を付与することが可能となる。
また、火災時に有毒ガスを発生するハロゲン化合物などの物質を用いないため、環境に対する負荷は極めて小さい。
ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide self-extinguishing property to an organic polymer product simply and at low cost, without reducing the physical property intrinsic | native to an organic polymer product.
In addition, since a halogen compound or the like that generates a toxic gas during a fire is not used, the burden on the environment is extremely small.
本発明を実施するための最良の形態を以下に説明する。
本発明の改質剤は、有機高分子製品に自己消火性を付与する改質剤であり、吸水性ポリマーの存在下で下記一般式（１）または（２）で示されるケイ素アルコキシドを加水分解重縮合したシロキサン化合物を含む溶液からなるものである。
［化１］
Si（OR）4 （１）
（式（１）中、Rはアルキル基を表す。また、アルキル基としては、炭素数１〜４のものが好ましい。）
［化２］
Si（OR）ｎ（X）４−ｎ （２）
（式（２）中、Rはアルキル基、Xはアルキル基、官能基を含むアルキル基またはハロゲンを表す。また、Xとしては、カルボニル基、カルボキシル基、アミノ基、ビニル基、またはエポキシ基を有するアルキル基が好適である。アルキル基としてはいずれも炭素数１〜４のものが好ましい。ｎは１〜４までの整数である。）
ここで、好ましいケイ素アルコキシドとしては、Si（OC２ H５）4、Si（OC H３）４が例示される。
The best mode for carrying out the present invention will be described below.
The modifier of the present invention is a modifier that imparts self-extinguishing properties to an organic polymer product, and hydrolyzes a silicon alkoxide represented by the following general formula (1) or (2) in the presence of a water-absorbing polymer. It consists of a solution containing a polycondensed siloxane compound.
[Chemical 1]
Si (OR) 4 (1)
(In formula (1), R represents an alkyl group. Moreover, as an alkyl group, a C1-C4 thing is preferable.)
[Chemical 2]
Si (OR) n (X) 4-n (2)
(In formula (2), R represents an alkyl group, X represents an alkyl group, an alkyl group containing a functional group, or a halogen. X represents a carbonyl group, a carboxyl group, an amino group, a vinyl group, or an epoxy group. (The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. N is an integer of 1 to 4.)
Here, preferable silicon alkoxides include Si (OC 2 H 5 ) 4 and Si (OC H 3 ) 4 .
一般的に、ケイ素アルコキシドの加水分解重縮合はゾル・ゲル法と呼ばれる反応の常法に従って行われる。より具体的には、ケイ素アルコキシドを水とエタノールなどのアルコールとの混合溶媒に溶かし、触媒としての塩酸などの酸、またはアンモニアなどのアルカリを添加して室温〜８０℃の温度で撹拌しながら反応させることである。 In general, hydrolytic polycondensation of silicon alkoxide is carried out in accordance with a conventional method called a sol-gel method. More specifically, silicon alkoxide is dissolved in a mixed solvent of water and an alcohol such as ethanol, an acid such as hydrochloric acid or an alkali such as ammonia is added as a catalyst, and the reaction is performed while stirring at a temperature of room temperature to 80 ° C. It is to let you.
本発明者らは、吸水性ポリマーの存在下でケイ素アルコキシドを加水分解重縮合したシロキサン化合物を含む溶液で、該シロキサン化合物の29Si-NMRによるスペクトルの帰属において、下記［数１］に示すように、Qｎ（ｎ＝０〜４）構造を示すシグナル（「ピーク」と同義。以下において、「ピーク」と記すこともある。）におけるQ４構造を示すシグナルの面積と、Q１、Q２、Q３構造を示すシグナルの面積の和との比が１．２０以下であることを特徴とするシロキサン化合物を含む溶液を改質剤として用いることによって、有機高分子製品に自己消火性を付与することができることを見出した。
［数１］
SQ４／(SQ１+ SQ２+ SQ３)≦１．２０
In the assignment of the spectrum by 29 Si-NMR of the siloxane compound in a solution containing a siloxane compound obtained by hydrolytic polycondensation of silicon alkoxide in the presence of a water-absorbing polymer, the present inventors have shown the following [Formula 1]. a, Q n (n = 0~4) signal indicative of the structure and the area of the signal indicative of the Q 4 structure in (a "peak" interchangeably. in the following, sometimes referred to as "peak".), Q 1, Q 2. By using a solution containing a siloxane compound as a modifier, the ratio of the signal area showing the Q 3 structure to the sum of the signal areas being 1.20 or less, the organic polymer product has self-extinguishing properties. It was found that it can be granted.
[Equation 1]
S Q4 / (S Q1 + S Q2 + S Q3 ) ≦ 1.20
本発明の有機高分子製品に自己消火性を付与する改質剤は、２９Si-NMR測定によって得られる前記シロキサン化合物のスペクトルから、ピークの範囲６７〜８０ppmにピークをもつQ0構造、ピークの範囲８０〜９０ppmにピークをもつQ1構造、ピークの範囲９０〜９６ppmにピークをもつQ２構造、ピークの範囲９７〜１０５ppmにピークをもつQ３構造およびピークの範囲１０５〜１１５ppmにピークをもつQ４構造のピーク面積を、それぞれ、SQ０、SQ１、SQ２、SQ３およびSQ４とし、SQ４とSQ１、SQ２、SQ３との和の比が１．２０以下であることを特徴とする。 The modifier for imparting self-extinguishing properties to the organic polymer product of the present invention has a Q 0 structure having a peak in the peak range of 67 to 80 ppm from the spectrum of the siloxane compound obtained by 29 Si-NMR measurement. Q 1 structure having a peak in the range of 80 to 90 ppm, Q 2 structure having a peak in the range of 90 to 96 ppm, Q 3 structure having a peak in the range of 97 to 105 ppm, and a peak in the range of 105 to 115 ppm the peak area of Q 4 structure, respectively, and S Q0, S Q1, S Q2 , S Q3 and S Q4, it S Q4 and S Q1, S Q2, the ratio of the sum of the S Q3 1.20 or less It is characterized by.
また、Q０〜Q４のピークの範囲はＮＭＲ測定法によって多少異なる。なお、ここでのシグナル（ピーク）の範囲は、溶液法測定チャートから読み取った範囲を記載している。
SQ４とSQ１、SQ２、SQ３との和の比が１．２０より大きい場合、Q４構造の究極であるシリカSiO２粒子に近いものが相当量生成されている。シリカ粒子は無機酸化物であり、それ自身燃えない。しかし、シリカには炭化皮膜形成能力がないために、有機高分子製品に自己消火性を付与するためには、多量のシリカが必要となる。そのため、重量が著しく増加し、また透明プラスチック製品の場合、透明性が損なわれるという問題が生じる。
一方、SQ４とSQ１、SQ２、SQ３との和の比が１．２０以下の場合、シリカ粒子に近いものが生成することは抑えられる。また、Q１〜Q３構造のシロキサン化合物が有機高分子の分子鎖との間に水素結合等によって相互作用して燃焼時に炭化皮膜が形成され、少量のシロキサン化合物によって有機高分子製品に自己消火性を付与することができると考えられる。
ここでQn構造とは、シリカの構成単位であるSiO4四面体単位の酸素原子のうちの架橋酸素原子（2つのSiと結合している酸素原子）の数に応じて決まる化学的構造をいい、QｎのnはSiO4単位の結合度であり、架橋酸素原子の数である。29Si-NMR測定によってQｎ構造を示すピークにおけるQ０、Q１、Q２、Q３、Q４構造を示すシグナルの面積をもとめることができる。
Further, the range of the peak of Q 0 to Q 4 are slightly different by NMR measurement. In addition, the range of the signal (peak) here has described the range read from the solution method measurement chart.
When the ratio of the sum of S Q4 and S Q1 , S Q2 , S Q3 is greater than 1.20, a considerable amount of particles close to the silica SiO 2 particles that are the ultimate of the Q 4 structure are generated. Silica particles are inorganic oxides and do not burn themselves. However, since silica does not have the ability to form a carbonized film, a large amount of silica is required to impart self-extinguishing properties to organic polymer products. Therefore, the weight increases remarkably, and in the case of a transparent plastic product, there arises a problem that transparency is impaired.
On the other hand, when the ratio of the sum of S Q4 and S Q1 , S Q2 , S Q3 is 1.20 or less, generation of a substance close to silica particles can be suppressed. Further, the siloxane compound of Q 1 to Q 3 structure carbide film during combustion interact by hydrogen bonding, etc. between the molecular chains of the organic polymer is formed, self-extinguishing organic polymer product with a small amount of the siloxane compound It is thought that sex can be imparted.
Here, the Q n structure is a chemical structure determined according to the number of bridging oxygen atoms (oxygen atoms bonded to two Si atoms) among the oxygen atoms of the SiO 4 tetrahedral unit, which is a structural unit of silica. Good, n in Qn is the degree of bonding of SiO 4 units and the number of bridging oxygen atoms. The area of the signal indicating the Q 0 , Q 1 , Q 2 , Q 3 , Q 4 structure in the peak indicating the Q n structure can be determined by 29 Si-NMR measurement.
具体的には、吸水性ポリマーの存在下でケイ素アルコキシドを加水分解重縮合したシロキサン化合物の29Si-NMRによるQｎ構造を示すシグナル（ピーク）の面積とQ１、Q２、Q３構造を示すシグナルの面積の和との比を下記［数２］に示す範囲、好ましくは下記［数３］に示す範囲、より好ましくは下記［数４］に示す範囲に制御することによって、有機高分子製品に自己消火性を付与することができる。
［数２］
０＜SQ4／(SQ1+ SQ2+ SQ3)≦１．２０
［数３］
０．１０≦SQ4／(SQ1+ SQ2+ SQ3)≦１．２０
［数４］
０．２０≦SQ4／(SQ1+ SQ2+ SQ3)≦０．９０
なお、シグナルの面積の制御は、加水分解縮合反応の温度および時間、ケイ素アルコキシドの量、反応後の保存温度および時間などによって制御できる。
Specifically, the area and Q 1, Q 2, Q 3 structure of a signal indicating the Q n structure with a silicon alkoxide in the presence of the water-absorbing polymer in 29 Si-NMR hydrolysis polycondensed siloxane compound (peak) By controlling the ratio of the signal area to the sum of the signal areas to the range shown in [Formula 2] below, preferably the range shown in [Formula 3] below, more preferably the range shown in [Formula 4] below, Self-extinguishing properties can be given to products.
[Equation 2]
0 <S Q4 / (S Q1 + S Q2 + S Q3 ) ≦ 1.20
[Equation 3]
0.10 ≦ S Q4 / (S Q1 + S Q2 + S Q3 ) ≦ 1.20
[Equation 4]
0.20 ≦ S Q4 / (S Q1 + S Q2 + S Q3 ) ≦ 0.90
The signal area can be controlled by the temperature and time of the hydrolysis condensation reaction, the amount of silicon alkoxide, the storage temperature and time after the reaction, and the like.
SQ4／(SQ1+ SQ2+ SQ3)を上記の範囲に制御することによって有機高分子製品に自己消火性を付与することができる機構は必ずしも明らかではないが、Q4構造の生成量を抑えることにより、自己消火性発現の大きな要因である燃焼時の炭化皮膜形成が起きやすくなることが重要な要因であることが推測される。 The mechanism that can give self-extinguishing properties to organic polymer products by controlling S Q4 / (S Q1 + S Q2 + S Q3 ) within the above range is not always clear, but the amount of Q 4 structure produced By suppressing the above, it is presumed that an important factor is that the formation of a carbonized film during combustion, which is a major factor in the expression of self-extinguishing properties, is likely to occur.
また、ケイ素アルコキシドを加水分解重縮合させた反応生成物を得る際に吸水性ポリマーを存在させることによって、有機高分子製品の自己消火性付与により適した溶液を得ることができる。 In addition, when a reaction product obtained by hydrolytic polycondensation of silicon alkoxide is obtained, the presence of a water-absorbing polymer makes it possible to obtain a solution more suitable for imparting self-extinguishing properties of organic polymer products.
用いる吸水性ポリマーは、ポリアクリル酸系、ポリビニルアルコール系、ポリ（N−ビニルアセトアミド）系、ポリアミノ酸系、ポリアクリルアミド系、ポリビニルピロリドン系、ポリヒドロキシエチルアクリレート系、ポリビニルメチルエーテル系、ポリ（イソブチレン−マレイン酸）系、ポリ（2−アクリルアミド−2−メチルプロパン−スルホン酸）系、ポリアクロキシプロパンスルホン酸系、ポリビニルホスホン酸系、ポリビニルピリジン系、ポリエチレングリコール系、ポリエチレンイミン系などの化学合成によって得られる吸水性ポリマーおよびアルギン酸、ポリグルタミン酸、ヒアルロン酸、カゼイン、コラーゲン、デンプン、ヒドロキシルセルロース、カルゲナンおよびこれらの金属塩、エステルなどの天燃物由来の吸水性ポリマーのうちいずれか一つまたはその組み合わせである。なかでもポリアクリル酸系、ポリアミノ酸系、ポリ（N−ビニルアセトアミド）系の吸水性ポリマーが好ましく、特に、ポリアクリル酸金属塩部分架橋体を主体とするポリアクリル酸系吸水性ポリマーが経済性の上で最も好ましい。 Water-absorbing polymers used are polyacrylic acid, polyvinyl alcohol, poly (N-vinylacetamide), polyamino acid, polyacrylamide, polyvinylpyrrolidone, polyhydroxyethyl acrylate, polyvinyl methyl ether, poly (isobutylene) -Chemical synthesis such as maleic acid), poly (2-acrylamido-2-methylpropane-sulfonic acid), polyacryloxypropanesulfonic acid, polyvinylphosphonic acid, polyvinylpyridine, polyethylene glycol, polyethyleneimine The resulting water-absorbing polymer and water-absorbing polymer derived from natural materials such as alginic acid, polyglutamic acid, hyaluronic acid, casein, collagen, starch, hydroxylcellulose, cargenan and their metal salts and esters It is any one or a combination Of chromatography. Of these, polyacrylic acid-based, polyamino acid-based, and poly (N-vinylacetamide) -based water-absorbing polymers are preferable, and polyacrylic acid-based water-absorbing polymers mainly composed of polyacrylic acid metal salt partially crosslinked products are economical. Most preferred above.
本発明において、ケイ素アルコキシドを加水分解重縮合させた反応生成物を得る際に吸水性ポリマーと無機微粒子を存在させることもできる。
用いる無機微粒子は、酸化チタン、酸化亜鉛、シリカ、アルミナ、酸化鉄などの金属酸化物、ベントナイト、タルク、カオリナイト、マイカ、ケイ酸カルシウム、モンモリロナイトなどのケイ酸塩、カーボンブラック、グラファイト、カーボンナノチューブ、カーボンナノコイルなどの炭素化合物、水酸化アルミニウム、水酸化マグネシウムなどの金属水酸化物、炭酸カルシウム、硫酸カルシウムなどの金属炭酸塩、鉄粉、銅粉、アルミニウム粉、などの金属粉、チタン酸カリウム、チタン酸ジルコン酸鉛、硫化モリブデンなどの中の一つまたはその組み合わせである。後述する金属アルコキシドの加水分解重縮合反応を行う際に触媒として塩酸などの酸を用いる場合は酸によって分解されない無機微粒子を用いる。また、金属アルコキシドの加水分解重縮合反応を行う際に触媒としてカセイソーダなどのアルカリを用いる場合はアルカリによって分解されない無機微粒子を用いる。これらの点を考慮して、酸化チタンなどの酸化物、タルク、カオリナイトなどのケイ酸塩を用いることが好ましい。また、用いる無機微粒子の平均粒径は１nmから１０mmの間であり、特に０．０１〜１０μmの範囲にあるものが好ましい。
In the present invention, when a reaction product obtained by hydrolytic polycondensation of silicon alkoxide is obtained, a water-absorbing polymer and inorganic fine particles may be present.
Inorganic fine particles used include metal oxides such as titanium oxide, zinc oxide, silica, alumina, and iron oxide, silicates such as bentonite, talc, kaolinite, mica, calcium silicate, and montmorillonite, carbon black, graphite, and carbon nanotubes , Carbon compounds such as carbon nanocoils, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, metal carbonates such as calcium carbonate and calcium sulfate, metal powders such as iron powder, copper powder and aluminum powder, titanic acid One or a combination of potassium, lead zirconate titanate, molybdenum sulfide and the like. In the case of using an acid such as hydrochloric acid as a catalyst when performing a hydrolysis polycondensation reaction of a metal alkoxide described later, inorganic fine particles that are not decomposed by the acid are used. Moreover, when using alkalis, such as caustic soda, as a catalyst when performing the hydrolysis polycondensation reaction of a metal alkoxide, the inorganic fine particle which is not decomposed | disassembled by an alkali is used. Considering these points, it is preferable to use oxides such as titanium oxide and silicates such as talc and kaolinite. The average particle size of the inorganic fine particles used is between 1 nm and 10 mm, and those in the range of 0.01 to 10 μm are particularly preferable.
また、本発明において、吸水性ポリマーの存在下でケイ素アルコキシドを加水分解重縮合させる際にシリコーン化合物を共存させることもできる。 In the present invention, a silicone compound can be allowed to coexist when hydrolytic polycondensation of silicon alkoxide in the presence of a water-absorbing polymer.
シリコーン化合物としてはジメチルポリシロキサン系シリコーンオイル、両末端変性ジメチルポリシロキサン系シリコーンオイルなどのシリコーンオイル、次式(A)、(B)、(C)で示される化学構造を有するシリコーン界面活性剤などを用いることができる。
Ｒ：アルキル基または水素
Ｒ’：アルキレン基
アルキル基としては、炭素数１〜１０のものが用いられることが好ましい。アルキレン基としては、炭素数１〜１０のものが用いられることが好ましい。また、ａは０〜１００、ｂは０〜１００、ｍは５〜１０００、ｎは１〜５０の範囲であるものが好ましい。さらに、東レダウコーニング（株）製シリコーン界面活性剤Ｌシリーズ、ＦＺシリーズなどを用いることが好ましい。
Silicone compounds include dimethylpolysiloxane-based silicone oil, silicone oils such as both-end-modified dimethylpolysiloxane-based silicone oil, silicone surfactants having a chemical structure represented by the following formulas (A), (B), and (C) Can be used.
また、本発明の改質剤には酸化防止剤、紫外線吸収剤、光安定剤、赤外線吸収剤、赤外線反射剤、防カビ剤、防腐剤、防蟻剤、防虫剤などの添加剤を添加することができる。これらの添加剤は、ケイ素アルコキシドに加水分解重縮合する工程で添加すること、或いは、加水分解重縮合が終了した後の溶液に添加することが可能である。
また、リン酸アンモニウムなどのリン系難燃剤、ホウ酸、ホウ砂などのホウ素系難燃剤などを減圧・加圧、溶融混練などの方法で有機高分子製品中に注入あるいは添加したものを改質剤によって改質することで、有機高分子製品の自己消火性をさらに向上させることもできる。
In addition, additives such as antioxidants, ultraviolet absorbers, light stabilizers, infrared absorbers, infrared reflectors, fungicides, antiseptics, anticides, and insecticides are added to the modifier of the present invention. be able to. These additives can be added in the step of hydrolytic polycondensation to silicon alkoxide, or can be added to the solution after completion of hydrolytic polycondensation.
In addition, modification is made by injecting or adding phosphorus-based flame retardants such as ammonium phosphate or boron-based flame retardants such as boric acid or borax into organic polymer products by methods such as decompression, pressurization, and melt-kneading. By modifying with an agent, the self-extinguishing property of the organic polymer product can be further improved.
吸水性ポリマーの存在下でケイ素アルコキシドを加水分解重縮合させて得られた改質剤を有機高分子製品に表面塗布または含浸することによって、自己消火性の有機高分子製品を得ることができる。
有機高分子製品としては木材製品、パーティクルボード、ファイバーボードなどの合板、木材と他素材との複合材料製品、竹材製品、紙製品、段ボール、畳表、天然ゴムなどの天然物系有機高分子製品およびプラスチック製品、合成ゴム製品などの非天然物系有機高分子製品が挙げられる。
プラスチックとしては熱可塑性樹脂、熱硬化性樹脂のいずれもが対象となり、これらの樹脂の射出成形体、押出成形体、中空成形体、回転成形体、発泡成形体などによる各種の成形法によって得られる計器パネルカバー、ランプカバーなどの自動車部品、電子・電気機器筐体および部品、フィルム、シート、ディスプレーカバー、プラスチックレンズ、光記録媒体など広範囲の製品を用いることができる。
ここで、レンズ、眼鏡、透明フィルム・シート、ディスプレーカバー、計器カバー、ランプカバーなどの用途に応用する場合は、ポリカーボネート、ポリメチルメタクリレートなどのアクリル樹脂、ポリエチレンテレフタレート、トリアセチルセルロース、ポリジエチレングリコールビスアリルカーボネート、シクロオレフィン系樹脂、ポリ乳酸およびこれらの共重合体あるいは変成体等の透明性のプラスチックを用いることが好ましい。
A self-extinguishing organic polymer product can be obtained by applying or impregnating the organic polymer product with a modifier obtained by hydrolytic polycondensation of silicon alkoxide in the presence of a water-absorbing polymer.
Organic polymer products include wood products, plywood such as particleboard and fiberboard, composite materials made of wood and other materials, bamboo products, paper products, cardboard, tatami mats, natural products such as natural rubber, and natural rubber. Non-natural organic polymer products such as plastic products and synthetic rubber products are listed.
Plastics include both thermoplastic resins and thermosetting resins, and can be obtained by various molding methods such as injection molded products, extruded molded products, hollow molded products, rotational molded products, and foam molded products. A wide range of products can be used such as automotive parts such as instrument panel covers and lamp covers, electronic and electrical equipment casings and parts, films, sheets, display covers, plastic lenses, optical recording media.
Here, for applications such as lenses, glasses, transparent films / sheets, display covers, instrument covers, lamp covers, etc., acrylic resins such as polycarbonate and polymethyl methacrylate, polyethylene terephthalate, triacetyl cellulose, polydiethylene glycol bisallyl It is preferable to use a transparent plastic such as carbonate, cycloolefin resin, polylactic acid, and a copolymer or modified product thereof.
また、筐体などの用途に応用する場合は、アクリロニトリル・スチレン・ブタジエン三元共重合樹脂（ＡＢＳ樹脂）、ポリアミド、ポリカーボネート、ポリカーボネート／ＡＢＳ樹脂系アロイ、変性ポリフェニレン、変性ポリフェニレン系アロイ、ポリプロピレン、ポリプロピレン／無機フィラー複合材料、コハク酸・１，４−ブタンジオール重縮合体、アジピン酸・１，４−ブタンジオール重縮合体、ポリ乳酸、コハク酸・１，４−ブタンジオール・乳酸重縮合体、アジピン酸・１，４−ブタンジオール・乳酸重縮合体、フェノール樹脂、不飽和ポリエステル、エポキシ樹脂、ポリイミド等を用いることが例示される。
また、ゴム製品の用途において、天然ゴム、イソプレンゴム、ブタジエンゴム、クロロプレンゴム、ブチルゴム、スチレンブタジエンゴム、二トリルゴムなどの加工製品を用いることが例示される。
For applications such as housing, acrylonitrile / styrene / butadiene terpolymer resin (ABS resin), polyamide, polycarbonate, polycarbonate / ABS resin alloy, modified polyphenylene, modified polyphenylene alloy, polypropylene, polypropylene / Inorganic filler composite material, succinic acid / 1,4-butanediol polycondensate, adipic acid / 1,4-butanediol polycondensate, polylactic acid, succinic acid / 1,4-butanediol / lactic acid polycondensate, Examples thereof include using adipic acid / 1,4-butanediol / lactic acid polycondensate, phenol resin, unsaturated polyester, epoxy resin, polyimide, and the like.
Examples of the use of rubber products include the use of processed products such as natural rubber, isoprene rubber, butadiene rubber, chloroprene rubber, butyl rubber, styrene butadiene rubber, and nitrile rubber.
本発明の改質剤による有機高分子製品の改質は、種々の手法により行うことができ、例えば、ディップコーティング、スプレーコーティング、スピンコーティング、ロールコーティング、スクリ―ン印刷、刷毛塗り、流し塗り、含浸処理等により行なうことができる。
ここで、レンズなどの高度の用途向けでは、１軸駆動装置を用いて引き上げ速度０．０１〜１．５０mm/秒で精密にディップコーティングを行なうことが好ましい。その際、コーティング溶液の温度、粘度を一定に管理し、駆動時の基板およびコーティング溶液にできるだけ振動を与えないようにすることが好ましい。
また、表面コーティングされた帯電防止膜の膜厚は０．０１〜１０．００μmの範囲、特に０．１０〜１．００μmの範囲であることが好ましい。
なお、ディップコーティングを行なう際には、片面を保護フィルムなどでマスキングして行なってもよい。
Modification of the organic polymer product with the modifier of the present invention can be performed by various methods, such as dip coating, spray coating, spin coating, roll coating, screen printing, brush coating, flow coating, It can be performed by impregnation treatment or the like.
Here, for advanced applications such as lenses, it is preferable to perform dip coating with a single-axis drive device at a pulling speed of 0.01 to 1.50 mm / sec. At that time, it is preferable that the temperature and viscosity of the coating solution are controlled to be constant so that the substrate and the coating solution are not vibrated as much as possible.
The surface-coated antistatic film preferably has a thickness in the range of 0.01 to 10.00 μm, particularly preferably in the range of 0.10 to 1.00 μm.
When performing dip coating, one side may be masked with a protective film or the like.
本発明の吸水性ポリマーの存在下でケイ素アルコキシドを加水分解重縮合したシロキサン化合物を含む溶液を、コーティング、刷毛塗り、含浸処理などを行った後に、自然乾燥または３０〜１５０℃の温度で、１０分〜２４時間、加熱乾燥することにより有機高分子製品に対してシロキサン化合物が０．０１〜５．００重量%含有された改質有機高分子製品を得ることができる。また、ディップコーティング、スプレーコーティングなどの方法を用いることによって、シロキサン化合物の含有量を０．０１〜３．００重量%に制御することもできる。 A solution containing a siloxane compound obtained by hydrolytic polycondensation of silicon alkoxide in the presence of the water-absorbing polymer of the present invention is subjected to coating, brushing, impregnation treatment, etc., followed by natural drying or at a temperature of 30 to 150 ° C. A modified organic polymer product containing 0.01 to 5.00% by weight of a siloxane compound with respect to the organic polymer product can be obtained by heating and drying for 24 minutes. Moreover, content of a siloxane compound can also be controlled to 0.01 to 3.00 weight% by using methods, such as dip coating and spray coating.
最良の形態の本発明によれば、例えば、０．０１〜５．００重量%、或いは０．０１〜３．００重量%、という少量のシロキサン化合物の含有量で有機高分子製品に自己消火性を付与することができる。このため、有機高分子製品の重量増加を最少限に抑えることができ、また物性低下の懸念がない。さらに、有機高分子製品中での化学反応を伴わないため、経済的に極めて有利である。 According to the best mode of the present invention, the self-extinguishing property of an organic polymer product can be obtained with a small amount of a siloxane compound, for example, 0.01 to 5.00% by weight, or 0.01 to 3.00% by weight. Can be granted. For this reason, an increase in the weight of the organic polymer product can be minimized, and there is no concern about deterioration of physical properties. Furthermore, since it does not involve chemical reaction in organic polymer products, it is extremely advantageous economically.
以下では、実施例により本発明の内容を具体的に説明するが、これらの実施例により本発明は何ら限定されるものではなく、上述した技術思想の範囲内で変更した任意の形態を実施可能であることは言うまでもない。 In the following, the contents of the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples, and any form modified within the scope of the technical idea described above can be implemented. Needless to say.
１００mlビーカーに水１３．００gとポリアクリル酸ナトリウム部分架橋体を主体とするポリアクリル酸系吸水性ポリマー粉末２５．００mgを入れ、室温で５分間撹拌した。その後、エタノール２５．００g、塩化水素０．７５g、テトラエトキシシラン１２．５０gを加えて室温で２時間撹拌した。
得られた反応液を室温で７日間放置した後に、日本電子製AL−４００を用いて29Si-NMRの測定を行った。測定は試料約3gに緩和試薬であるCr(acac)3を約15mg加えて３０分間よく振って混合溶解させた後、１０mmφテフロン（登録商標）製NMR試料管に入れた。また、内管にはテトラメチルシランを重アセトンで溶解した液を５mmφテフロン封管に高さ５cm程度入れたものを使用した。
測定された29Si-NMRスペクトルの帰属において、下記［数５］に示すように、Q１、Q２、Q３、Q４構造を示すシグナルにおけるQ４構造を示すシグナルの面積と、Q１、Q２、Q３構造を示すシグナルの面積の和との比は０．４０であった。
なお、Q１、Q２、Q３、Q４構造におけるそれぞれのシグナルの面積は、SQ１＝０．９０、SQ2＝６．３０、SQ３＝６５．２０、SQ４＝２９．００である。
［数５］
SQ4／(SQ1+ SQ2+ SQ3)＝０．４０
A 100 ml beaker was charged with 13.00 g of water and 25.00 mg of a polyacrylic acid-based water-absorbing polymer powder mainly composed of a partially crosslinked sodium polyacrylate, and stirred at room temperature for 5 minutes. Thereafter, 25.00 g of ethanol, 0.75 g of hydrogen chloride and 12.50 g of tetraethoxysilane were added and stirred at room temperature for 2 hours.
The resulting reaction solution was allowed to stand at room temperature for 7 days, and then 29 Si-NMR was measured using AL-400 manufactured by JEOL. For the measurement, about 15 mg of Cr (acac) 3 as a relaxation reagent was added to about 3 g of the sample, and the mixture was thoroughly mixed and dissolved for 30 minutes. The inner tube used was a solution obtained by dissolving tetramethylsilane in heavy acetone into a 5 mmφ Teflon sealed tube with a height of about 5 cm.
In the assignment of the measured 29 Si-NMR spectrum, as shown in [Equation 5] below, the area of the signal showing the Q 4 structure in the signal showing the Q 1 , Q 2 , Q 3 , Q 4 structure, and Q 1 , Q 2 , Q 3 ratio to the sum of signal areas indicating structures was 0.40.
The area of each signal in the Q 1 , Q 2 , Q 3 , and Q 4 structures is S Q1 = 0.90, S Q2 = 6.30, S Q3 = 65.20, and S Q4 = 29.00. is there.
[Equation 5]
S Q4 / (S Q1 + S Q2 + S Q3 ) = 0.40
反応終了後、７日間室温で放置した反応液を用いて、スギおよびヒノキの試験片（長さ１００mm、幅７５mm、厚さ５mm）の全面にスプレーコーティングした。
さらに、コーティング後、２日間自然乾燥した後で重量を測定し、反応前の重量と比較した。その結果、スギには１．４重量%、ヒノキには１．６重量%のシロキサン化合物がコーティングされていることが認められた。
After completion of the reaction, the reaction solution left at room temperature for 7 days was spray coated on the entire surface of a cedar and cypress specimen (length 100 mm, width 75 mm, thickness 5 mm).
Further, after coating, the weight was measured after air drying for 2 days and compared with the weight before reaction. As a result, it was confirmed that cedar was coated with 1.4% by weight of siloxane compound and cypress was coated with 1.6% by weight of siloxane compound.
このようにして、改質されたスギおよびヒノキ試験片について、直径１．７cmの都市ガスバーナーで外炎高さ１０cm、内炎高さ６cmの炎で燃焼試験を行った。その結果を表１に示す。 The cedar and cypress specimens thus modified were subjected to a combustion test using a city gas burner having a diameter of 1.7 cm and a flame having an outer flame height of 10 cm and an inner flame height of 6 cm. The results are shown in Table 1.
［比較例１］
改質を施さないスギおよびヒノキの試験片について実施例1と同じ燃焼試験を行った。その結果を表１に示す。
[Comparative Example 1]
The same burning test as in Example 1 was performed on the cedar and cypress specimens not subjected to modification. The results are shown in Table 1.
以上のとおり、実施例１の改質剤をコーティングすることにより、着火時間を遅延できることが確認できた。すなわち、改質木材は未改質木材と比べて着火に至るまでの時間が長く、未改質木材とは異なるように、着火後にバーナーの炎を離すと自己消火する自己消火性をもつことが確認できた。 As described above, it was confirmed that the ignition time could be delayed by coating the modifier of Example 1. In other words, modified wood takes longer to ignite than unmodified wood, and unlike unmodified wood, it has a self-extinguishing property that self-extinguishes when the burner flame is released after ignition. It could be confirmed.
水１２．００gとポリアクリル酸ナトリウム部分架橋体を主体とするポリアクリル酸系吸水性ポリマー粉末２０．００mgとを１００mlビーカーに入れ、室温で５分間撹拌した。さらに酸化チタン微粒子（ルチル型、平均一次粒径０．２０μm）１０．００mgを加え、室温で５分間撹拌した後にエタノール３０．００g、塩化水素０．７５g、テトラエトキシシラン１２．５０gを加えて室温で２時間撹拌した。得られた反応液を室温で２日間放置した後に、実施例１と同様の方法で29Si-NMRの測定を行った。
測定された29Si-NMRスペクトルの帰属において、下記［数６］に示すように、Q1、Q2、Q3、Q4構造を示すシグナルにおけるQ4構造を示すシグナルの面積と、Q1、Q2、Q3構造を示すシグナルの面積の和との比は０．３０であった。
なお、Q1、Q2、Q3、Q4構造におけるそれぞれのシグナルの面積は、SQ１＝１．００、SQ2＝１３．７０、SQ３＝５８．１０、SQ４＝２２．２０である。
［数６］
SQ4／(SQ1 + SQ2+ SQ3)＝０．３０
12.00 g of water and 20.00 mg of a polyacrylic acid-based water-absorbing polymer powder mainly composed of a sodium polyacrylate partially crosslinked product were placed in a 100 ml beaker and stirred at room temperature for 5 minutes. Further, 10.00 mg of titanium oxide fine particles (rutile type, average primary particle size 0.20 μm) were added and stirred at room temperature for 5 minutes, and then 30.00 g of ethanol, 0.75 g of hydrogen chloride and 12.50 g of tetraethoxysilane were added to room temperature. For 2 hours. The obtained reaction solution was allowed to stand at room temperature for 2 days, and then 29 Si-NMR was measured in the same manner as in Example 1.
In the assignment of the measured 29 Si-NMR spectrum, as shown in [Formula 6] below, the area of the signal indicating the Q 4 structure in the signal indicating the Q 1 , Q 2 , Q 3 , Q 4 structure, and Q 1 , Q 2 , Q 3 ratio to the sum of signal areas indicating structures was 0.30.
The areas of the signals in the Q 1 , Q 2 , Q 3 , and Q 4 structures are S Q1 = 1.00, S Q2 = 13.70, S Q3 = 58.10, and S Q4 = 22.20. is there.
[Equation 6]
S Q4 / (S Q1 + S Q2 + S Q3 ) = 0.30
反応終了後２日間室温で放置した反応液を用いて、スギおよびヒノキの試験片（長さ１００mm、幅７５mm、厚さ５mm）の全面にスプレーコーティングした。さらに、コーティング後、２日間自然乾燥した後で重量を測定し、反応前の重量と比較した。
その結果、スギには１．５０重量%、ヒノキには１．７０重量%のシロキサン化合物がコーティングされていることが認められた。
Using the reaction solution left at room temperature for 2 days after the completion of the reaction, spray coating was performed on the entire surface of cedar and cypress test pieces (length 100 mm, width 75 mm, thickness 5 mm). Further, after coating, the weight was measured after air drying for 2 days and compared with the weight before reaction.
As a result, it was confirmed that cedar was coated with 1.50% by weight of siloxane compound and cypress was coated with 1.70% by weight of siloxane compound.
このようにして改質されたスギおよびヒノキ試験片について、実施例１と同様の方法で燃焼試験を行った。その結果を表２に示す。 The cedar and cypress test pieces thus modified were subjected to a combustion test in the same manner as in Example 1. The results are shown in Table 2.
［比較例２］
実施例２と同じ組成の原料を用いて、ゾル・ゲル反応を行った。その際に、反応温度を５０℃、反応時間を３時間とした反応液および反応温度を６０℃、反応時間を３時間とした反応液を作製した。
反応終了２日後に、これらの反応液について、実施例１と同様の方法で29Si-NMRの測定、木材へのスプレーコーティングおよび燃焼試験を行った。得られた結果を表２に示す。
A sol-gel reaction was performed using raw materials having the same composition as in Example 2. At that time, a reaction solution having a reaction temperature of 50 ° C. and a reaction time of 3 hours and a reaction solution having a reaction temperature of 60 ° C. and a reaction time of 3 hours were prepared.
Two days after the completion of the reaction, these reaction solutions were subjected to 29 Si-NMR measurement, spray coating on wood, and combustion test in the same manner as in Example 1. The obtained results are shown in Table 2.
以上のとおり、実施例２の改質剤をコーティングすることにより、着火時間を遅延できることが確認できた。すなわち、改質スギ(2)と改質ヒノキ(2)とは着火に至るまでの時間が長く、着火後にバーナーの炎を離すと自己消火する自己消火性をもつことが確認できた。
また、改質スギ(3)、(4)および改質ヒノキ(3)、(4)は着火に至るまでの時間がやや短く、着火後にバーナーの炎を離すと自己消火する自己消火性をもたないことが確認できた。
As described above, it was confirmed that the ignition time could be delayed by coating the modifier of Example 2. That is, it was confirmed that the modified cedar (2) and the modified hinoki (2) had a long time to ignition, and had a self-extinguishing property that self-extinguishes when the burner flame was released after ignition.
The modified cedar (3) and (4) and the modified cypress (3) and (4) have a slightly shorter time to ignition, and have self-extinguishing properties that self-extinguish when the burner flame is released after ignition. It was confirmed that there was not.
実施例２と同じ反応液において、反応終了後２日間室温で放置した反応液を用いて、紙ダンボールの試験片（長さ１００mm、幅７５mm、厚さ２mm）に含浸処理した後、自然乾燥して改質紙ダンボールを得た。また、この改質紙ダンボールにはシロキサン化合物が４．００重量%コーティングされていることが認められた。
この改質紙ダンボールについて、実施例１と同様の方法で燃焼試験を行った。得られた結果を表３に示す。
In the same reaction solution as in Example 2, a test piece of paper cardboard (length 100 mm, width 75 mm, thickness 2 mm) was impregnated with the reaction solution left at room temperature for 2 days after completion of the reaction, and then naturally dried. The modified paper cardboard was obtained. In addition, it was confirmed that the modified paper cardboard was coated with 4.00% by weight of a siloxane compound.
This modified paper cardboard was subjected to a combustion test in the same manner as in Example 1. The obtained results are shown in Table 3.
［比較例３］
改質を施さない紙ダンボールの試験片について実施例３と同様の方法で燃焼試験を行った。得られた結果を表３に示す。
[Comparative Example 3]
A combustion test was performed in the same manner as in Example 3 on a test piece of paper cardboard that was not modified. The obtained results are shown in Table 3.
以上のとおり、実施例３の改質剤をコーティングすることにより、着火時間を遅延できることが確認できた。すなわち、改質ダンボールは未改質ダンボールと比べて着火に至るまでの時間が長く、着火後にバーナーの炎を離すと自己消火する自己消火性をもつことが示された。 As described above, it was confirmed that the ignition time could be delayed by coating the modifier of Example 3. That is, it was shown that the modified cardboard has a longer time to ignition than the unmodified cardboard and has a self-extinguishing property that self-extinguishes when the burner flame is released after ignition.
ポリアクリル酸系吸水性ポリマー６０．００mgに水４０．００gを加え、室温で５分間撹拌した。次に別容器にエチルアルコール６０．００gと式（Ａ）のシリコ―ン界面活性剤０．４０gを加え、室温で５分間撹拌した。吸水性ポリマーを含む水溶液にシリコ―ン界面活性剤を含むエチルアルコールを加え、さらにテトラエトキシシラン４２．５０g、ギ酸２．２５gを加えて室温で１．５時間攪拌した後に３日間室温で放置した。
このようにして調製した反応液を容量２００mlのビーカーに入れ、ポリカーボネート押出成形品をカットして得られた平板（５０×５０×０．８mm）を反応液に浸した。その後、１軸駆動装置を用いて１．０mm／秒の速度で反応液から引き上げて精密ディップコーティングをおこなった。表面コーティングされて得られた改質ポリカーボネ―ト平板を２４時間自然放置して乾燥した。また、シロキサン化合物のコーティング量は０．１２重量%であった。
調整された反応液については、実施例１と同様の方法で29Si-NMRの測定を行った。測定された29Si-NMRスペクトルの帰属において、下記［数７］に示すように、Q1、Q2、Q3、Q4構造を示すシグナルにおけるQ4構造を示すシグナルの面積と、Q1、Q2、Q3構造を示すシグナルの面積の和との比は０．２８であった。
なお、Q1、Q2、Q3、Q4構造におけるそれぞれのシグナルの面積は、SQ１＝３．００、SQ2＝２７．３０、SQ３＝４７．７０、SQ４＝２２．００である。
［数７］
SQ4／(SQ1 + SQ2+ SQ3)＝０．２８
また、得られた改質ポリカーボネート(1)平板について実施例１と同様の方法で燃焼試験を行った。得られた結果を表４に示す。
40.00 g of water was added to 60.00 mg of the polyacrylic acid water-absorbing polymer, and the mixture was stirred at room temperature for 5 minutes. Next, 60.00 g of ethyl alcohol and 0.40 g of a silicone surfactant of the formula (A) were added to another container and stirred at room temperature for 5 minutes. Ethyl alcohol containing a silicone surfactant was added to an aqueous solution containing a water-absorbing polymer, 42.50 g of tetraethoxysilane and 2.25 g of formic acid were added, and the mixture was stirred at room temperature for 1.5 hours and then allowed to stand at room temperature for 3 days. .
The reaction solution thus prepared was put into a beaker having a capacity of 200 ml, and a flat plate (50 × 50 × 0.8 mm) obtained by cutting a polycarbonate extruded product was immersed in the reaction solution. After that, precision dip coating was performed by pulling up from the reaction solution at a speed of 1.0 mm / sec using a single-axis driving device. The modified polycarbonate flat plate obtained by surface coating was left to stand for 24 hours and dried. The coating amount of the siloxane compound was 0.12% by weight.
For the prepared reaction solution, 29 Si-NMR was measured in the same manner as in Example 1. In the assignment of the measured 29 Si-NMR spectrum, as shown in [Equation 7] below, the area of the signal indicating the Q 4 structure in the signal indicating the Q 1 , Q 2 , Q 3 , Q 4 structure, and Q 1 , Q 2 , Q 3 ratio to the sum of the areas of the signals indicating the structure was 0.28.
The areas of the signals in the Q 1 , Q 2 , Q 3 , and Q 4 structures are S Q1 = 3.00, S Q2 = 27.30, S Q3 = 47.70, and S Q4 = 22.00. is there.
[Equation 7]
S Q4 / (S Q1 + S Q2 + S Q3 ) = 0.28
Further, the obtained modified polycarbonate (1) flat plate was subjected to a combustion test in the same manner as in Example 1. Table 4 shows the obtained results.
〔比較例４〕
改質を施さないポリカーボネート平板について実施例３と同様の方法で燃焼試験を行った。その結果は表４に示す通りである。
また、実施例４と同じ組成の原料を用いて、ゾル・ゲル反応を行った。その際に、反応温度を５０℃、反応時間を３時間とした反応液および反応温度を６０℃、反応時間を３時間とした反応液を作製した。
また、反応終了３日後に、これらの反応液について、実施例４と同様の方法で29Si-NMRの測定、木材へのスプレーコーティングおよび燃焼試験を行った。得られた結果を表４に示す。
[Comparative Example 4]
A combustion test was performed on the polycarbonate flat plate not subjected to modification in the same manner as in Example 3. The results are as shown in Table 4.
Further, a sol-gel reaction was performed using raw materials having the same composition as in Example 4. At that time, a reaction solution having a reaction temperature of 50 ° C. and a reaction time of 3 hours and a reaction solution having a reaction temperature of 60 ° C. and a reaction time of 3 hours were prepared.
Further, 3 days after the completion of the reaction, these reaction solutions were subjected to 29 Si-NMR measurement, spray coating on wood, and combustion test in the same manner as in Example 4. Table 4 shows the obtained results.
以上のとおり、実施例４の改質剤をコーティングすることにより、着火時間を遅延できることが確認できた。すなわち、改質ポリカーボネート(1)は着火に至るまでの時間が長く、着火後にバーナーの炎を離すと自己消火する自己消火性をもつことが確認できた。
また、改質ポリカーボネート(2)、(3)は着火に至るまでの時間がやや短く、着火後にバーナーの炎を離すと自己消火する自己消火性をもたないことが確認できた。
As described above, it was confirmed that the ignition time could be delayed by coating the modifier of Example 4. That is, it was confirmed that the modified polycarbonate (1) has a long time to ignition, and has a self-extinguishing property that self-extinguishes when the burner flame is released after ignition.
In addition, it was confirmed that the modified polycarbonates (2) and (3) had a slightly shorter time to ignition, and did not have a self-extinguishing property that self-extinguishes when the burner flame is released after ignition.
本発明は、有機高分子製品を用いる全ての産業に利用することができ、例えば、住宅産業、自動車産業などでの利用が想定される。
有機高分子製品が木材である場合について説明すると、日本の森林が荒廃し始めている。その大きな要因として木材の需要が低迷していることが挙げられる。この状況を打破するには木材の需要を拡大させることが必要不可欠である。
これに対して既に国を挙げていろいろな対策が講じられている。たとえば国土交通省は平成１２年に建築基準法を改定し、従来は可燃物という認識から外装材などの重要建築材料への使用を禁じていた木材に対して不燃、難燃の性能が規定に合格すれば使用を認めることとし、木材の大口需要への道を開いた。また文部科学省は木材環境が児童生徒の心身に良い影響をもたらすという認識の下に最近校舎の木造化を推進しようとしている。
しかしながら木材に含浸あるいは注入された表面劣化防止材、木材保存剤、難燃剤などが雨水によって容易に溶脱して木材の耐久性が損なわれてしまうために、木材の需要分野はほとんど拡大していないのが現状である。
本発明の成果を利用することによって木材が本来有している調湿性を維持したまま、高度の表面劣化防止性、防カビ・防虫・防蟻性、難燃性を長期間にわたって有する高機能木材製品が実用化可能となる。その結果住宅、校舎などの外装材、ドアなどここ数十年間法規制などのために我が国では使用実績が乏しかった用途分野に木材が大量に使用できる道が開け、木材産業の振興に大きく貢献できることが期待される。また木材の需要が大きく増大することによって、日本の森林再生にも大きく貢献することが期待される。
The present invention can be used in all industries that use organic polymer products, and is expected to be used in, for example, the housing industry and the automobile industry.
To explain the case where the organic polymer product is wood, Japanese forests are beginning to be devastated. A major factor is the sluggish demand for timber. To overcome this situation, it is essential to increase the demand for wood.
In response, various measures have already been taken across the country. For example, the Ministry of Land, Infrastructure, Transport and Tourism revised the Building Standards Act in 2000, and in the past, wood was prohibited from being used as an important building material such as an exterior material because it was recognized as a flammable material. If it passes, it will be approved for use, paving the way for large-scale demand for wood. The Ministry of Education, Culture, Sports, Science and Technology has recently been trying to promote the building of school buildings in recognition that the timber environment has a positive impact on the mind and body of children and students.
However, the demand field of wood has hardly expanded because surface deterioration prevention materials, wood preservatives, flame retardants, etc. impregnated or injected into wood are easily leached by rainwater and the durability of the wood is impaired. is the current situation.
By using the results of the present invention, highly functional wood having a high degree of surface deterioration prevention, mold prevention, insect prevention, ant protection, and flame retardancy over a long period of time while maintaining the moisture conditioning inherent to the wood. The product can be put into practical use. As a result, it is possible to greatly contribute to the promotion of the timber industry by opening up a way to use a large amount of timber in fields of use that have not been used in Japan due to laws and regulations such as exterior materials and doors such as houses and school buildings for the past several decades. There is expected. In addition, the demand for timber is expected to greatly contribute to Japan's forest restoration.
Claims (7)
［化１］
Si（OR） 4 （１）
（式（１）中、Rは炭素数１〜４のアルキル基を表す。）
で表されるケイ素アルコキシドを加水分解重縮合したシロキサン化合物を含む溶液であって、該シロキサン化合物が、その２９Si-NMR測定スペクトルの帰属において、Qｎ（ｎ＝０〜４）構造を示すシグナルにおけるQ４構造を示すシグナルの面積と、Q１、Q２、Q３構造を示すシグナルの面積の和との比SQ４/（SQ１＋SQ２＋SQ３）が０．２以上０．９０以下であることを特徴とするコーティング、塗布、含浸または加圧注入することにより木材、ダンボールまたはプラスチック製品に自己消火性を付与する改質剤。
ここでQｎ構造とは、シリカの構成単位であるSiO4四面体単位の酸素原子のうちの架橋酸素原子（2つのSiと結合している酸素原子）の数に応じて決まる化学的構造をいい、QnのnはSiO４単位の結合度であり、架橋酸素原子の数である。 In the presence of a water-absorbing polymer, the following general formula (1)
[Chemical 1]
Si (OR) 4 (1)
(In formula (1), R represents an alkyl group having 1 to 4 carbon atoms.)
A signal containing a siloxane compound obtained by hydrolytic polycondensation of a silicon alkoxide represented by the formula: wherein the siloxane compound has a Q n (n = 0 to 4) structure in the assignment of its 29 Si-NMR measurement spectrum. The ratio S Q4 / (S Q1 + S Q2 + S Q3 ) of the signal area showing the Q 4 structure and the sum of the signal areas showing the Q 1 , Q 2 , and Q 3 structures is 0.2 or more and 0.90 or less A modifier which imparts self-extinguishing properties to wood, cardboard or plastic products by coating, applying, impregnating or pressure injecting .
Here, Q n structure, the chemical structure depends on the number of bridging oxygen atoms of the oxygen atom of the SiO 4 tetrahedral units is a structural unit of the silica (oxygen atom bonded to two Si) Good, n in Qn is the degree of bonding of SiO 4 units and the number of bridging oxygen atoms.
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| US9707742B2 (en) | 2011-11-14 | 2017-07-18 | Nitto Denko Corporation | Flame-resistant composite member |
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