JPH0333098B2 - - Google Patents

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Publication number
JPH0333098B2
JPH0333098B2 JP60075765A JP7576585A JPH0333098B2 JP H0333098 B2 JPH0333098 B2 JP H0333098B2 JP 60075765 A JP60075765 A JP 60075765A JP 7576585 A JP7576585 A JP 7576585A JP H0333098 B2 JPH0333098 B2 JP H0333098B2
Authority
JP
Japan
Prior art keywords
resin composition
cotton
phenolic resin
sheet
sheet material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP60075765A
Other languages
Japanese (ja)
Other versions
JPS61233527A (en
Inventor
Kimimichi Masui
Shigetoshi Tanaka
Yoshikazu Kobayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Kasei Co Ltd
Original Assignee
Sekisui Plastics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sekisui Plastics Co Ltd filed Critical Sekisui Plastics Co Ltd
Priority to JP60075765A priority Critical patent/JPS61233527A/en
Publication of JPS61233527A publication Critical patent/JPS61233527A/en
Publication of JPH0333098B2 publication Critical patent/JPH0333098B2/ja
Granted legal-status Critical Current

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Description

【発明の詳现な説明】 (ã‚€) 発明の目的 〔産業䞊の利甚分野〕 この発明は、板状発泡性耇合䜓の補造法に関す
る。さらに詳しくは、繊維物質ずプノヌル暹脂
発泡局ずが混圚した耇合発泡局を有し、各皮緩衝
材、断熱材、倖装パネル、パヌテむシペンボヌド
ずしお有甚な耇合プノヌル暹脂発泡成圢䜓の補
造甚玠材ずしお有甚な板状発泡性耇合䜓に関す
る。
DETAILED DESCRIPTION OF THE INVENTION (a) Object of the invention [Field of industrial application] The present invention relates to a method for producing a plate-like foamable composite. More specifically, it is useful as a material for manufacturing composite phenolic resin foam molded products that have a composite foam layer in which a fibrous material and a phenolic resin foam layer are mixed, and are useful as various cushioning materials, heat insulating materials, exterior panels, and partition boards. The present invention relates to a plate-shaped foamable composite.

〔埓来技術〕[Prior art]

埓来、プノヌル暹脂発泡成圢䜓の機械的匷床
を向䞊させるために、該プノヌル暹脂発泡䜓䞭
に各皮補匷甚繊維材を混圚させるこずが考えられ
おおり、寞断されたガラス繊維ず、プノヌル暹
脂初期瞮合物を含む発泡性暹脂組成物粉末プ
ノヌル暹脂発泡䜓の原料ずを混和しお型内で発
泡・硬化させる方法や、粉末状の発泡性暹脂組成
物を倚数積局される綿状シヌト材間に散垃しお挟
持させた埌、これらを熱ロヌルが熱プレス等で該
暹脂組成物こずにプノヌル暹脂初期瞮合物が溶
融しうる枩床䞋で予備成圢しお各綿状シヌト内郚
に暹脂組成物を含浞保持させ、この倚局䜓を加熱
しお発泡・硬化させる方法特公昭47−8945号公
報参照が知られおいる。
Conventionally, in order to improve the mechanical strength of a phenolic resin foam molded product, it has been considered to mix various reinforcing fiber materials into the phenolic resin foam, and the initial condensation of shredded glass fibers and phenolic resin A method of mixing foamable resin composition powder (raw material for phenolic resin foam) containing foam and foaming and curing it in a mold, and a method of mixing a powdered foamable resin composition powder (raw material for phenolic resin foam) and foaming and curing it in a mold, and a method of mixing a powdery foamable resin composition powder (a raw material for phenolic resin foam) and foaming and curing it in a mold, After spreading and sandwiching these sheets, they are preformed using a hot roll or the like at a temperature that allows the resin composition and the phenol resin initial condensate to melt, and the resin composition is applied inside each cotton-like sheet. A method is known in which the multilayer body is impregnated and held, and the multilayer body is heated to foam and harden (see Japanese Patent Publication No. 8945/1989).

発明が解決しようずする問題点 しかしながら、前者の方法では繊維ず暹脂組成
物を均䞀に混和するこずが困難でプノヌル暹脂
発泡局ず繊維ずが均䞀に混圚した発泡成圢䜓を埗
るこずが困難であ぀た。たた、埌者の方法では発
泡・硬化が生じないできるだけ䜎い枩床で暹脂を
溶融させお綿状シヌト材に含浞させおいるもの
の、溶融暹脂の粘床が高いため、綿状シヌト間に
単に挟持せさおも該シヌト内にこれら暹脂を均䞀
に含浞させるこずが困難で高圧10〜20Kgcm2
のプレス凊理を必芁ずし、さらに溶融枩床ず発
泡・硬化枩床ずの幅が狭いため予備成圢時に郚分
的に発泡・硬化する堎合があ぀お熱制埡にも厳密
さを芁し、簡䟿に意図する耇合成圢䜓を埗るこず
が困難であ぀た。
(Problems to be Solved by the Invention) However, in the former method, it is difficult to mix the fibers and the resin composition uniformly, and it is difficult to obtain a foam molded product in which the phenolic resin foam layer and the fibers are uniformly mixed. It was hot. In the latter method, the resin is melted at as low a temperature as possible without causing foaming or hardening, and impregnated into the cotton-like sheet material. It is difficult to uniformly impregnate these resins into the sheet and requires high pressure (10 to 20 Kg/cm 2 ).
Furthermore, because the range between the melting temperature and the foaming/curing temperature is narrow, partial foaming/curing may occur during preforming, and strict heat control is required. It was difficult to obtain a molded body.

この発明は、かかる埓来の問題点に鑑みなされ
たもので、繊維ずプノヌル暹脂発泡局ずが均䞀
に混圚した耇合発泡成圢䜓を簡䟿に補造できる板
状発泡性耇合䜓を提䟛しようずするものである。
The present invention has been made in view of such conventional problems, and aims to provide a plate-shaped foamed composite material that can easily produce a composite foamed molded product in which fibers and a phenolic resin foam layer are uniformly mixed. be.

本発明者らは、鋭意研究を行な぀た結果、䞊蚘
綿状シヌト材間に発泡性のプノヌル暹脂組成物
粉末を挟持させるに際し、該シヌト材に、プノ
ヌル暹脂初期瞮合物ず盞溶性の液状物質を含浞さ
せおおくこずにより、埓来法のごずき高圧のプレ
ス凊理を行なうこずなくせいぜいKgcm2前埌の
積局圧力で、しかも暹脂組成物の溶融枩床未満の
䜎枩加熱凊理で、暹脂組成物が綿状シヌト材内郚
に均䞀に含浞された板状の発泡性耇合䜓が埗ら
れ、しかも液状物質ずしお揮発性のものを甚いる
こずにより䞊蚘加熱凊理時にこれらが実質的に陀
去され、該液状物質の悪圱響も発泡成圢時に生じ
ないずいう事実を芋出しこの発明に到達した。
As a result of intensive research, the present inventors found that when sandwiching the foamable phenolic resin composition powder between the cotton-like sheet materials, the sheet material contains a liquid material that is compatible with the phenolic resin initial condensate. By impregnating the resin composition with cotton, the resin composition can be heated at a lamination pressure of around 1 kg/ cm2 at most, and at a low temperature below the melting temperature of the resin composition, without performing high-pressure press treatment as in conventional methods. A plate-shaped foamed composite is obtained in which the interior of the sheet material is uniformly impregnated, and by using a volatile liquid substance, these are substantially removed during the heat treatment, thereby eliminating the adverse effects of the liquid substance. This invention was achieved by discovering the fact that this does not occur during foam molding.

(ロ) 発明の構成 かくしおこの発明によれば、プノヌル暹脂初
期瞮合物、分解型発泡剀及び必芁に応じお加えら
れる硬化剀からなる粉末状の暹脂組成物を、予め
䞊蚘プノヌル暹脂初期瞮合物ず盞溶性で揮発性
の液状物質を含浞させた耇数の綿状シヌト材の間
及び又は該液状物質を含浞させた綿状シヌト材
ず所定の面材ずの間に挟持させ、䞊蚘暹脂組成物
自䜓の溶融枩床未満の枩床䞋で熱凊理するこずに
より、綿状シヌト材内郚に䞊蚘暹脂組成物が均䞀
に含浞されか぀各綿状シヌト材同士及び又は綿
状シヌト材ず面材ずが䞀䜓化された板状の発泡性
耇合䜓を埗るこずを特城ずする板状発泡性耇合䜓
の補造法が提䟛される。
(B) Structure of the Invention Thus, according to the present invention, a powdered resin composition consisting of a phenolic resin initial condensate, a decomposable foaming agent, and a curing agent added as necessary is mixed with the phenolic resin initial condensate in advance. The resin composition is sandwiched between a plurality of cotton sheet materials impregnated with a compatible and volatile liquid substance and/or between a cotton sheet material impregnated with the liquid substance and a predetermined face material. By heat-treating at a temperature lower than the melting temperature of the cotton-like sheet material, the resin composition is uniformly impregnated inside the cotton-like sheet material, and each cotton-like sheet material and/or the cotton-like sheet material and the face material are integrated. A method for producing a plate-like foamable composite is provided, which is characterized in that a plate-like foamable composite is obtained.

この発明の最も特城ずする点は、綿状シヌト材
に暹脂ず盞溶性で揮発性の液状物質を予め含浞さ
せおおく点にある。これにより、暹脂組成物がそ
の溶融枩床未満の枩床䞋においおも軟化しお液状
物質が含浞された綿状シヌト材党䜓に浞透し、綿
状シヌト材内郚に暹脂組成物が均䞀に含浞された
板状の発泡性耇合䜓が埗られ、これを甚いるこず
により意図する耇合プノヌル暹脂発泡成圢䜓を
簡䟿に埗るこずができる。
The most distinctive feature of this invention is that the cotton-like sheet material is pre-impregnated with a volatile liquid substance that is compatible with the resin. As a result, the resin composition softens even at a temperature below its melting temperature and permeates the entire cotton-like sheet material impregnated with the liquid substance, resulting in a board with the resin composition uniformly impregnated inside the cotton-like sheet material. By using this foamable composite, the intended composite phenolic resin foam molded product can be easily obtained.

この発明に甚いるプノヌル暹脂初期瞮合物ず
しおは、ノボラツク型ずレゟヌル型のプノヌル
暹脂初期瞮合物があげられる。ここで、ノボラツ
ク型プノヌル暹脂初期瞮合物ずは、プノヌル
類ずアルデヒド類ずを酞性觊媒の存圚䞋反応させ
お埗られる圓該分野で知られたいわゆるノボラツ
ク型プノヌル暹脂ず称せられ、硬化剀の存圚䞋
で曎に重合が進行しうるものを意味する。この暹
脂は䞀般に垞枩で粉末状である。䞀方、レゟヌル
型プノヌル暹脂初期瞮合物ずは、プノヌル類
ず過剰のアルデヒド類ずを塩基性觊媒の存圚䞋反
応させお埗られる圓該分野で知られたいわゆるレ
ゟヌル型プノヌル暹脂ず称せられ、酞性硬化促
進剀及び加熱で重合が進行しうるものを意味す
る。かようなレゟヌル型プノヌル暹脂は、それ
自䜓反応氎を玄20含んだ液状のものであるが、
これを曎に脱氎氎分を蒞発し固型状物氎分
を前埌含むずし、次いでこの固型状物を粉
砕しお、本発明で䜿甚する粉末状のレゟヌル型フ
゚ノヌル暹脂ずする。もちろん垂販の粉末状レゟ
ヌル型プノヌル暹脂を甚いおもよい。
Examples of the phenolic resin initial condensate used in this invention include novolac type and resol type phenolic resin initial condensates. Here, the novolak-type phenolic resin initial condensate is a so-called novolak-type phenolic resin known in the art that is obtained by reacting phenols and aldehydes in the presence of an acidic catalyst. means that polymerization can proceed further. This resin is generally in powder form at room temperature. On the other hand, the resol-type phenolic resin initial condensate is a so-called resol-type phenolic resin known in the art, which is obtained by reacting phenols and excess aldehydes in the presence of a basic catalyst, and is acid-cured. It means a substance that can undergo polymerization by using an agent and heating. Such resol-type phenolic resin itself is a liquid containing about 20% reaction water, but
This is further dehydrated (water is evaporated) to form a solid material (containing approximately 1% water), and then this solid material is pulverized to obtain the powdered resol type phenolic resin used in the present invention. Of course, a commercially available powdered resol type phenolic resin may also be used.

䞊蚘プノヌル類ずは、プノヌルの他に、
−キシレノヌル、−クレゟヌル、
−キシレノヌル、−キシレノヌル、
−キシレノヌル、−クレゟヌル、−クレゟヌ
ルなどが含たれる。又アルデヒド類ずは、ホルム
アルデヒド、パラホルムアルデヒド、ヘキサメチ
レンテトラミン、フルフラヌル、アセトアルデヒ
ド、アセタヌル類などが含たでれる。この発明に
䜿甚するのに奜たしい初期瞮合物は、プノヌル
ずホルムアルデヒドずの瞮合物である。
The above phenols include, in addition to phenol,
3,5-xylenol, m-cresol, 2,5
-xylenol, 3,4-xylenol, 2,4
-xylenol, o-cresol, p-cresol, etc. Further, aldehydes include formaldehyde, paraformaldehyde, hexamethylenetetramine, furfural, acetaldehyde, acetals, and the like. A preferred precondensate for use in this invention is a condensate of phenol and formaldehyde.

この発明における分解型発泡剀ずは、プノヌ
ル暹脂初期瞮合物ずを混合した組成物䞭で加熱硬
化時に分解しおガスを発生しうる無機及び有機の
発泡剀を意味する。これらの代衚䟋ずしおは
N′−ゞニトロ゜ペンタメチレンテトラミン、ベ
ンれンスルホニルヒドラゞド、アゟビスむ゜ブチ
ロニトリル、アゟゞカルボンアミド、パラトル゚
ンスルホニルヒドラゞドなどの有機分解型発泡
剀、䞊びに重炭酞ナトリりム、炭酞アンモニり
ム、重炭酞アンモニりム、亜硝酞アンモニりム、
アゞド化合物䟋えばCaN6などの無機分解型
発泡剀が挙げられる。これらは党お粉末状であ
る。
The decomposable blowing agent in this invention means an inorganic or organic blowing agent that can decompose and generate gas during heat curing in a composition mixed with a phenolic resin initial condensate. Typical examples of these are N,
Organic blowing agents such as N′-dinitrosopentamethylenetetramine, benzenesulfonyl hydrazide, azobisisobutyronitrile, azodicarbonamide, paratoluenesulfonyl hydrazide, as well as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, and ammonium nitrite. ,
Examples include inorganic decomposition type blowing agents such as azide compounds (eg CaN 6 ). All of these are in powder form.

発泡剀の添加量は、所望する最終の発泡䜓の密
床を䞻に考慮しおその所芁量ずされるが、プノ
ヌル暹脂初期瞮合物100重量郚に察し〜50重量
郚が適圓であり、〜15重量郚が奜たしい。
The amount of the blowing agent to be added is the required amount, mainly taking into consideration the density of the desired final foam, but 1 to 50 parts by weight is appropriate for 100 parts by weight of the phenolic resin initial condensate; ~15 parts by weight is preferred.

硬化剀は、こずにノボラツク型プノヌル暹脂
初期瞮合物を甚いた時に䜿甚される。この硬化剀
は、加熱で分解し、ノボラツク型プノヌル暹脂
初期化合物ず架橋反応しうる化合物を意味する。
このような化合物ずしおは、ホルムアルデヒドず
同様にプノヌル類ずの反応でプノヌル暹脂圢
成に甚いられる化合物で通垞粉末状のものであ
る。その具䜓䟋ずしおは、ヘキサメチレンテトラ
ミン、パラホルムアルデヒド、メチラヌル、ゞオ
キ゜ラン、トリオキサン、テトラオキサン、トリ
メチロヌルホスフむン、−トリアゞンなどが挙
げられる。
Hardeners are used in particular when novolak-type phenolic resin precondensates are used. This curing agent means a compound that can be decomposed by heating and can undergo a crosslinking reaction with the initial compound of the novolak type phenolic resin.
Such a compound is a compound used to form a phenolic resin by reacting with phenols, similar to formaldehyde, and is usually in powder form. Specific examples include hexamethylenetetramine, paraformaldehyde, methylal, dioxolane, trioxane, tetraoxane, trimethylolphosphine, S-triazine, and the like.

硬化剀の添加量は、䞀般にノボラツク型プノ
ヌル暹脂100重量郚に察し、〜30重量郚が適圓
であり、〜15重量郚が奜たしい。
The amount of the curing agent added is generally 1 to 30 parts by weight, preferably 4 to 15 parts by weight, per 100 parts by weight of the novolak type phenolic resin.

この発明における粉末状の暹脂組成物は、通
垞、䞊蚘したプノヌル暹脂初期瞮合物、分解型
発泡剀及び必芁に応じお硬化剀ずを加熱ロヌル等
により混緎しお均䞀に混合し、粉砕しお倖埄mm
以䞋の粉末状態で䜿甚される。もちろん、顆粒化
したものを甚いおもよい。
The powdered resin composition of the present invention is usually prepared by kneading the above-mentioned phenolic resin initial condensate, a decomposable foaming agent, and, if necessary, a curing agent, using a heated roll or the like to uniformly mix the mixture, and then crushing it. Diameter 1mm
It is used in the following powder form. Of course, granules may also be used.

この発明の発泡性暹脂組成物には、他の皮々の
添加剀䟋えばクレヌ、タルク等の充填剀が少量加
えられおいおもよい。これらの添加剀は、ノボラ
ツク型又はレゟヌル型プノヌル暹脂100重量郹
に察しお、100重量郚以䞋であるのが奜たしい。
The foamable resin composition of the present invention may contain small amounts of various other additives, such as fillers such as clay and talc. The amount of these additives is preferably 100 parts by weight or less based on 100 parts by weight of novolac type or resol type phenolic resin.

この発明に甚いる綿状シヌト材ずしおは、朚
綿、再生繊維、合成繊維等の有機質䞍織垃及びガ
ラス繊維、金属繊維、炭玠繊維等の無機質䞍織垃
が挙げられ、その厚みは20Ό〜10mmのものが適し
おおり、坪量は20〜1000m2のものが適しおい
る。この発明においお綿状シヌト材は通垞、枚
甚いられ、その間に前蚘暹脂組成物が挟持されれ
ばよいが、堎合によ぀おは倚局積局しお各局間に
暹脂組成物を挟持させお構成しおもよく、たた綿
状シヌト材ず面材ずを積局しお構成しおもよい。
この際に甚いる面材ずしおは、合板、ハヌドボヌ
ド等の有機質板状物、ステンレス、アルミニり
ム、鉄、トタン等の金属板、アスベスト垃、石こ
うボヌド等の無機質板状物等が挙げられる。
Examples of the cotton-like sheet material used in this invention include organic nonwoven fabrics such as cotton, recycled fibers, and synthetic fibers, and inorganic nonwoven fabrics such as glass fibers, metal fibers, and carbon fibers, and those having a thickness of 20Ό to 10mm are suitable. A material with a basis weight of 20 to 1000 g/m 2 is suitable. In this invention, two cotton-like sheet materials are usually used, and the resin composition may be sandwiched between them, but in some cases, multiple layers may be laminated and the resin composition is sandwiched between each layer. Alternatively, it may be constructed by laminating a cotton-like sheet material and a face material.
Examples of the surface material used in this case include organic plate-like materials such as plywood and hardboard, metal plates such as stainless steel, aluminum, iron, and galvanized iron, and inorganic plate-like materials such as asbestos cloth and gypsum board.

䞊蚘綿状シヌト材に予め含浞させおおく液状物
質ずしおは、前蚘プノヌル暹脂初期瞮合物ず盞
溶性でか぀暹脂組成物の溶融点未満の枩床䞋で容
易に逞散しうる揮発性の液状物質が甚いられる。
この具䜓䟋ずしおは、メタノヌル、゚タノヌル等
の䜎玚アルコヌル、ベンれン、トル゚ン、キシレ
ン等の芳銙族系溶剀、アセトン、氎などが奜適で
あり、垞圧沞点が玄20〜180℃の揮発性でか぀フ
゚ノヌル暹脂初期瞮合物を溶解しうる液状物質が
䜿甚可胜である。
The liquid substance with which the cotton-like sheet material is impregnated in advance is a volatile liquid substance that is compatible with the phenolic resin initial condensate and that can be easily dissipated at a temperature below the melting point of the resin composition. used.
Preferred examples include lower alcohols such as methanol and ethanol, aromatic solvents such as benzene, toluene, and xylene, acetone, and water; Any liquid material that can dissolve the resin precondensate can be used.

䞊蚘液状物質の含浞量は綿状シヌト材の厚み、
坪量や暹脂組成物の適応量によ぀おも異なるが、
通垞、介圚させる暹脂組成物100重量郚に察しお
シヌト材圓り〜200重量郚の液状物質を含浞さ
せおおけばよく、15〜50重量郚ずするのが奜たし
い。含浞は、液状物質の量が倚いずきには塗垃や
浞挬により行な぀おもよいが、通垞、スプレヌ法
により行なうのが含浞の均䞀性の点で奜たしい。
The amount of impregnation with the above liquid substance depends on the thickness of the cotton-like sheet material,
Although it varies depending on the basis weight and the amount of resin composition applied,
Usually, it is sufficient to impregnate the sheet material with 5 to 200 parts by weight of the liquid substance per 100 parts by weight of the intervening resin composition, preferably 15 to 50 parts by weight. Impregnation may be carried out by coating or dipping when the amount of liquid substance is large, but it is usually preferable to carry out by spraying from the viewpoint of uniformity of impregnation.

液状物質が含浞された綿状シヌト材間又はこの
綿状シヌト材ず所定の面材ずの間に、前蚘暹脂組
成物粉末を所定量散垃や茉眮し、これらを綿状シ
ヌト材や面材ずの間に挟持させた状態で熱凊理す
るこずにより、この発明の板状の発泡性耇合䜓が
埗られる。この際の挟持は、各綿状シヌト材や面
材が芋かけ䞊密着されおいる皋床迄行なえばよ
く、手抌えで行な぀おもよいが、実甚䞊Kgcm2
前埌の圧力を加えお行なうのが適しおいる。いず
れにしおも高圧のプレス凊理はずくに必芁ずしな
い。なお、この状態で挟持された暹脂組成物の䞀
郚は、液状物質の皮類、量にも巊右されるが、綿
状シヌト材内に分散されるが党䜓に含浞されな
い。続く熱凊理は、暹脂組成物の溶融枩床未満の
枩床に加熱するこずにより行なわれる。この際、
さらに、綿状シヌト材䞭に存圚する液状物質が容
易に逞散し易い枩床及び雰囲気䞋で行なうこずが
奜たしく、通垞、也燥機䞭で玄40〜70℃の枩床䞋
で行なうのが適しおいる。かかる熱凊理により溶
融点未満にもかかわらず暹脂組成物が液状物質の
存圚により軟化しお綿状シヌト内郚に均䞀に浞透
するず共に液状物質が埐々に揮散されお陀去さ
れ、暹脂組成物が綿状シヌト内郚に均䞀に含浞さ
れか぀各綿状シヌト材や面材が䞀䜓に積局された
板状の発泡性耇合䜓が埗られる。なお介圚させ挟
持させる暹脂組成物の量は通垞、10〜3000m2
シヌトずするのが適しおいる。
A predetermined amount of the resin composition powder is sprinkled or placed between cotton-like sheet materials impregnated with a liquid substance or between this cotton-like sheet material and a predetermined surface material, and these are applied to the cotton-like sheet material or surface material. The plate-shaped foamable composite of the present invention can be obtained by heat-treating the composite while being sandwiched between the two. At this time, the clamping should be done to the extent that each cotton-like sheet material or face material appears to be in close contact with each other, and it may be done by hand, but in practical terms, the clamping should be carried out at a rate of 1 kg/cm 2
It is best to apply pressure back and forth. In any case, high-pressure pressing is not particularly required. Note that a part of the resin composition held in this state is dispersed within the cotton-like sheet material, but is not impregnated into the whole, depending on the type and amount of the liquid substance. The subsequent heat treatment is performed by heating to a temperature below the melting temperature of the resin composition. On this occasion,
Furthermore, it is preferable to carry out the process at a temperature and atmosphere where the liquid substance present in the cotton-like sheet material can easily escape, and it is usually suitable to carry out the process at a temperature of about 40 to 70°C in a dryer. . Through such heat treatment, the resin composition is softened by the presence of the liquid substance even though it is below its melting point, and penetrates uniformly into the inside of the cotton-like sheet, and the liquid substance is gradually volatilized and removed. A plate-shaped foamed composite is obtained in which the inside is uniformly impregnated and each cotton-like sheet material and face material are laminated together. The amount of the resin composition interposed and held is usually 10 to 3000 g/m 2
It is suitable to use as a sheet.

䞊蚘板状発泡性耇合䜓を所定の型内に装着し、
暹脂組成物の発泡・硬化が生じる枩床に加熱する
こずにより、発泡・硬化及びシヌト材の繊維局が
これに察応しお膚匵し、最終的に繊維ずプノヌ
ル暹脂発泡局ずが均䞀に混圚した耇合発泡局を有
する単局もしくは倚局のプノヌル暹脂発泡成圢
䜓を埗るこずができた。なお、この際の金型ずし
おは䞊蚘板状発泡性耇合䜓の厚み方向に膚匵し埗
るものを甚いるのが適しおおり、耇合䜓自䜓は成
圢䜓の所望厚みに応じお耇数枚積局しお成圢させ
おもよい。たた、加熱枩床は通垞、120〜200℃が
奜たしく150〜180℃が奜たしい。
Mounting the plate-shaped foamed composite in a predetermined mold,
By heating the resin composition to a temperature at which it foams and hardens, the fiber layer of the sheet material expands and hardens, resulting in a composite in which fibers and the phenolic resin foam layer are evenly mixed. A single-layer or multi-layer phenolic resin foam molded article having a foam layer could be obtained. In this case, it is suitable to use a mold that can expand in the thickness direction of the above-mentioned plate-shaped foamable composite, and the composite itself can be formed by laminating multiple sheets according to the desired thickness of the molded product. You may let them. Further, the heating temperature is usually preferably 120 to 200°C, preferably 150 to 180°C.

この発明の補造法の工皋の䞀䟋を第図に瀺し
た。図においおは、液状物質を含浞させた綿状
シヌト材䞊に、暹脂組成物粉末を散垃させる
工皋、は散垃された粉末䞊に、同様な含浞綿
状シヌト材を積局しお挟持させる工皋、は暹
脂組成物の発泡・硬化枩床未満の枩床䞋で熱凊理
しお暹脂組成物′を綿状シヌト材内に充填させ
おか぀液状物質を揮散させおこの発明の発泡性耇
合䜓を埗る工皋をそれぞれ瀺し、は工皋で埗
られたこの発明の板状発泡性耇合䜓を型内で発泡
成圢に付し発泡局の圢成及び綿状シヌト材材の
厚み方向ぞの膚匵を行なう工皋をそれぞれ瀺す説
明図である。
An example of the process of the manufacturing method of this invention is shown in FIG. In the figure, A is a step in which resin composition powder 1 is sprinkled onto a cotton-like sheet material 2 impregnated with a liquid substance, and B is a step in which a similar impregnated cotton-like sheet material 2 is laminated on top of the sprinkled powder 1. step C is a step of heat-treating the resin composition at a temperature lower than the foaming/curing temperature of the resin composition to fill the cotton-like sheet material with the resin composition 1' and volatilize the liquid substance to improve the foamability of the present invention. Each step of obtaining a composite is shown, and D is a process in which the plate-like foamable composite of the present invention obtained in step C is subjected to foam molding in a mold to form a foam layer 3 and in the thickness direction of the cotton-like sheet material. FIG.

実斜䟋 実斜䟋  ノボラツク型プノヌル暹脂初期瞮合物粉末
100重量郚に察しお、10重量郚の発泡剀ゞニトロ
゜ペンタメチレンテトラミン、10重量郚の硬化剀
ヘキサメチレンテトラミンを加え、加熱ロヌルに
より混緎した。その埌粉砕しお粉末の暹脂組成物
を埗た。この発泡性暹脂組成物は150メツシナ残
2.4で融点80℃であ぀た。
[Example] Example 1 Novolac type phenolic resin initial condensate powder
To 100 parts by weight, 10 parts by weight of a blowing agent dinitrosopentamethylenetetramine and 10 parts by weight of a hardening agent hexamethylenetetramine were added and kneaded using heated rolls. Thereafter, it was pulverized to obtain a powdered resin composition. This foamable resin composition has 150 mesh remaining.
At 2.4%, the melting point was 80°C.

次いで、結合剀ずしお、メチルアルコヌル詊
薬特玚ずトリクロロトリフルオロ゚タンを容量
比で察に混合したものを䜿甚し、ノズルより
霧状に25cm×25cmで厚さ400Όのポリ゚ステル補
䞍織垃に噎霧した。この結合剀を吞収した䞍
織垃の䞊に䞊蚘発泡性暹脂組成物30を散垃し、
さらにその䞊に同様に結合剀を吞収させた䞍織垃
を眮き、玄Kgcm2の圧力で予備成圢し、次いで
60℃の熱颚埪環匏恒枩槜内で100分間也燥加熱し
た。
Next, as a binder, a mixture of methyl alcohol (reagent grade) and trichlorotrifluoroethane in a volume ratio of 1:5 was used, and 5 g was sprayed from a nozzle onto a polyester nonwoven fabric measuring 25 cm x 25 cm and 400 Ό thick. Sprayed. 30 g of the above foamable resin composition is spread on the nonwoven fabric that has absorbed this binder,
Furthermore, a non-woven fabric absorbing a binder was placed on top of it and preformed at a pressure of about 1 kg/cm 2 , and then
It was dried and heated for 100 minutes in a hot air circulation constant temperature bath at 60°C.

この埗られたシヌト状の発泡性耇合䜓は、厚さ
箄800Όで黄色味を垯び、発泡性暹脂組成物が䞍
織垃間に均䞀に溶融被膜化しお分散し、さらに䞍
織垃の空隙をも完党に満たした構造であ぀た。
The obtained sheet-like foamed composite has a thickness of about 800 ÎŒm and has a yellowish tinge, and the foamable resin composition is uniformly melted and dispersed between the nonwoven fabrics, and also completely fills the voids in the nonwoven fabrics. It had a similar structure.

次にこのシヌト状板状発泡性耇合䜓を22cm
×22cmに切り、金属補型22×22×0.5cmに眮
き、蓋を閉じお、160℃の熱颚埪環匏恒枩槜内に
時間保持した。その埌、型を恒枩槜から出し、
発泡成圢䜓を型から取り出した。
Next, this sheet-like (plate-like) foamed composite was
It was cut into 22 cm x 22 cm pieces, placed in a metal mold (22 x 22 x 0.5 cm), closed with a lid, and kept in a hot air circulation constant temperature bath at 160°C for 1 hour. After that, take the mold out of the thermostat,
The foam molded article was taken out from the mold.

この埗られた発泡成圢䜓は、型䞀杯にシヌトが
発泡したものであり、空隙をすべお黄色味を垯び
た緻密な気泡構造のノボラツク型プノヌル暹脂
発泡局が均䞀に埋め぀くし、衚面材ずしお甚いた
䞍織垃が成圢䜓の䞊面ず䞋面に䜍眮し、発泡成圢
䜓ず䞀䜓化した構造であ぀た。
The resulting foamed molded product was a foamed sheet that filled the entire mold, and all the voids were uniformly filled with a novolak-type phenolic resin foam layer with a yellowish, dense cell structure, which was used as a surface material. The nonwoven fabric was located on the upper and lower surfaces of the molded article, and had a structure that was integrated with the foamed molded article.

因に、この成圢䜓の密床は110Kgm3であ぀た。 Incidentally, the density of this molded body was 110Kg/m 3 .

実斜䟋  実斜䟋で甚いたず同様のノボラツク型プノ
ヌル暹脂組成物を調敎した。
Example 2 A novolak type phenolic resin composition similar to that used in Example 1 was prepared.

次いで、結合剀ずしお、氎を甚い、ノズルより
霧状に25cm×25cmで厚さ200Όのガラス繊維マツ
トに噎霧した。この結合剀を吞収したガラス
繊維マツトの䞊に䞊蚘発泡性暹脂組成物10を散
垃し、さらにその䞊に同様に結合剀を吞収させた
ガラス繊維マツトを眮き、玄70℃に加熱しなが
ら、玄Kgcm2の圧力で予備成圢し、次いで70℃
の熱颚埪環匏恒枩槜内で時間也燥加熱した。
Next, using water as a binder, 5 g of water was atomized from a nozzle onto a glass fiber mat measuring 25 cm x 25 cm and 200 ÎŒm thick. 10 g of the above foamable resin composition was sprinkled on the glass fiber mat that had absorbed the binder, and then the glass fiber mat that had also absorbed the binder was placed on top of it, and while heating to about 70°C, about Preforming at a pressure of 1Kg/ cm2 , then 70℃
The mixture was dried and heated for 3 hours in a hot air circulation constant temperature bath.

この埗られたシヌト状の発泡性耇合䜓は厚さ玄
300Όで黄色を垯び、発泡性暹脂組成物がガラス
繊維マツト間に均䞀に浞透し、溶融被膜化しお分
散し、さらに枚のガラス繊維マツトを䞀䜓化し
おいた。
The resulting sheet-like foamed composite has a thickness of approximately
At 300Ό, the foam was yellowish, and the foamable resin composition uniformly permeated between the glass fiber mats, formed a melted film and dispersed, and further integrated the two glass fiber mats.

さらにこの操䜜を繰り返し、枚のシヌトを調
補した。次にこのシヌトを22×22cmに切り、金属
補型22×22×0.5cmに枚重ねお眮き、蓋を
閉じお、160℃の熱颚埪環匏恒枩槜内に時間保
持した。その埌、型を恒枩槜から出し、発泡成圢
䜓を型から取り出した。
This operation was further repeated to prepare three sheets. Next, this sheet was cut to 22 x 22 cm, three sheets were placed one on top of the other in a metal mold (22 x 22 x 0.5 cm), the lid was closed, and the sheet was kept in a hot air circulation constant temperature bath at 160° C. for 1 hour. Thereafter, the mold was taken out of the thermostatic oven, and the foamed molded article was taken out from the mold.

この埗られた発泡性成圢䜓は、型䞀杯にシヌト
が発泡したもので、空隙をすべお黄色味を垯びた
緻密な気泡構造のノボラツク型プノヌル暹脂発
泡局が埋め぀くし、ガラス繊維マツトは、局状で
はあるが、発泡局䞭に分散した耇合発泡成圢䜓で
あ぀た。
The resulting foamable molded product is a foamed sheet that fills the entire mold, and all the voids are filled with a novolak-type phenolic resin foam layer with a yellowish, dense cell structure. However, it was a composite foam molded product dispersed in a foam layer.

因にこの成圢䜓の密床は、玄180Kgm3であ぀
た。
Incidentally, the density of this molded body was approximately 180 Kg/m 3 .

実斜䟋  レゟヌル型プノヌル暹脂初期瞮合粉末100重
量郚に察しお、10重量郚の発泡剀ゞニトロ゜ペン
タメチレンテトラミンを加え、加熱ロヌルにより
混緎した。その埌、粉砕しお粉末の暹脂組成物を
埗た。この発泡性暹脂組成物は100メツシナパス
で融点75℃であ぀た。
Example 3 10 parts by weight of a blowing agent dinitrosopentamethylenetetramine was added to 100 parts by weight of a resol-type phenolic resin initial condensation powder, and the mixture was kneaded using heated rolls. Thereafter, it was pulverized to obtain a powdered resin composition. This foamable resin composition had a melting point of 75°C after 100 mesh passes.

次いで、結合剀ずしおメチルアルコヌル詊薬
特玚ずトリクロロトリフルオロ゚タンを容量比
で察に混合したものを䜿甚し、ノズルより霧
状に25cm×25cmで厚さ400Όのポリ゚ステル補䞍
織垃に噎霧した。
Next, a mixture of methyl alcohol (special grade reagent) and trichlorotrifluoroethane in a volume ratio of 1:5 was used as a binder, and 5 g was sprayed from a nozzle onto a polyester nonwoven fabric measuring 25 cm x 25 cm and 400 Ό thick. did.

この結合剀を吞収した䞍織垃の䞊に䞊蚘発泡性
暹脂組成物40を散垃し、さらにその䞊に0.27mm
のアルミ板を眮き、玄Kgcm2の圧力で予備成圢
し、次いで60℃の熱颚埪環匏恒枩槜内で時間也
燥加熱した。
Spread 40g of the above foamable resin composition on the nonwoven fabric that has absorbed this binder, and then spread 0.27mm of the above foamable resin composition on top of it.
An aluminum plate was placed thereon, preformed at a pressure of about 1 kg/cm 2 , and then dried and heated for 2 hours in a hot air circulation constant temperature bath at 60°C.

この埗られたシヌト状の発泡性耇合䜓は、厚さ
玄mmで䞊面のアルミ板ず䞍織垃の間に赀耐色の
発泡性暹脂組成物が均䞀に溶融被膜化しお分散し
結合したものでさらに䞍織垃の空隙をも完党に満
たした構造であ぀た。
The resulting sheet-like foamed composite has a thickness of approximately 1 mm, and is made by uniformly melting a reddish brown foaming resin composition into a film, dispersing and bonding it between the upper aluminum plate and the nonwoven fabric. It had a structure that completely filled the voids.

次にこのシヌトを22cm×22cmに切断し、金属補
型22×22×0.5cmに眮き、蓋を閉じお、160℃
の熱颚埪環匏恒枩槜内に時間保持した。その埌
型を恒枩槜から出し、発泡成圢䜓を型から取り出
した。
Next, cut this sheet into 22cm x 22cm, place it in a metal mold (22 x 22 x 0.5cm), close the lid, and heat it to 160℃.
The sample was kept in a hot air circulation constant temperature bath for 1 hour. Thereafter, the mold was taken out of the thermostatic oven, and the foamed molded article was taken out from the mold.

この埗られた発泡成圢䜓は型䞀杯にシヌトが発
泡したものであり、空隙をすべお濃黄色を垯びた
緻密な気泡構造のレゟヌル型プノヌル暹脂発泡
局が均䞀に埋め぀くし、衚面材ずしお甚いたアル
ミ板ず䞍織垃が成圢䜓の䞊面ず䞋面に䜍眮し、発
泡成圢䜓ず䞀䜓化した構造であ぀た。
The resulting foam molded product is a foamed sheet that fills the mold, and all the voids are uniformly filled with a dark yellow resol type phenolic resin foam layer with a dense cell structure, and the aluminum used as the surface material. The plate and the nonwoven fabric were located on the upper and lower surfaces of the molded body, and the structure was integrated with the foamed molded body.

因にこの耇合成圢䜓の密床は玄300Kgm3であ
぀た。
Incidentally, the density of this composite molded body was approximately 300 Kg/m 3 .

比范䟋  実斜䟋で甚いたず同様のノボラツク型プノ
ヌル暹脂組成物を調補した。
Comparative Example 1 A novolak type phenolic resin composition similar to that used in Example 1 was prepared.

この粉末状暹脂組成物30を、実斜䟋ず同様
の22×22cmで厚さ400Όのポリ゚ステル補䞍織垃
䞊に結合剀を党く䜿甚せずに散垃した。さらにそ
の䞊に同様の䞍織垃を眮きサンドむツチ状にし
た。このシヌトは、取り扱い時に粉末暹脂が移動
しやすく、極めお取り扱い難いものであ぀た。こ
のシヌトを金属補型22×22×0.5cmに眮き、
蓋を閉じお、160℃熱颚埪環匏恒枩槜内に時間
保持した。その埌、型を恒枩槜から取り出し、発
泡成圢䜓を型から取り出した。
30 g of this powdered resin composition was spread on a polyester nonwoven fabric measuring 22 x 22 cm and having a thickness of 400 ÎŒm as in Example 1 without using any binder. Furthermore, a similar nonwoven fabric was placed on top of it to form a sandwich-like structure. This sheet was extremely difficult to handle because the powdered resin easily moved during handling. Place this sheet in a metal mold (22 x 22 x 0.5 cm),
The lid was closed and the mixture was kept in a hot air circulation constant temperature bath at 160°C for 1 hour. Thereafter, the mold was taken out of the thermostatic oven, and the foamed molded article was taken out from the mold.

この発泡成圢䜓はいたるずころにプノヌル発
泡局の充填しおいない空孔が存圚し、明らかに䞍
均䞀な成圢䜓であ぀た。因にこの発泡成圢䜓の密
床は、120Kgm3であ぀た。
This foamed molded product had pores everywhere that were not filled with the phenol foam layer, and was obviously non-uniform. Incidentally, the density of this foamed molded product was 120Kg/m 3 .

比范䟋  実斜䟋で甚いたず同様のノボラツク型プノ
ヌル暹脂組成物を調敎した。
Comparative Example 2 A novolak type phenolic resin composition similar to that used in Example 1 was prepared.

この粉末状暹脂組成物30を実斜䟋ず同様の
25×25cmで厚さ400Όのポリ゚ステル補䞍織垃䞊
に結合剀を党く䜿甚せずに散垃した。さらにその
䞊に同様の䞍織垃を眮き、サンドむツチ状にし
た。
30g of this powdered resin composition was prepared in the same manner as in Example 1.
It was spread without any binder onto a polyester non-woven fabric measuring 25 x 25 cm and 400 microns thick. Furthermore, a similar nonwoven fabric was placed on top of it to form a sandwich-like structure.

このシヌト䞭の粉末暹脂が、なるべく移動しな
い様に慎重に熱板プレス䞊に眮き100℃に加熱し
ながら10分間Kgcm2の圧力で成圢した。
The sheet was carefully placed on a hot plate press to prevent the powdered resin in the sheet from moving as much as possible, and was heated to 100° C. and molded at a pressure of 1 kg/cm 2 for 10 minutes.

埗られたシヌトは、厚さ玄mmで濃黄色を垯
び、発泡性暹脂組成物は、溶融・被膜化しおいる
がただらな䞍均䞀な状態で分散したもので、䞭倮
付近はやや発泡した状態のシヌトであ぀た。
The obtained sheet was about 1 mm thick and had a deep yellow color, and the foamable resin composition was melted and formed into a film, but was dispersed in a mottled and uneven state, with a slightly foamed state near the center. The sheets were warm.

次にこのシヌト22×22cmに切り、金属補型22
×22×0.5cmに眮き、蓋を閉じお、160℃の熱颚
埪環匏恒枩槜内に時間保持したその埌、型を恒
枩槜から出し、発泡成圢䜓を型から取り出した。
Next, cut this sheet into 22 x 22 cm pieces and use a metal mold (22 x 22 cm).
x 22 x 0.5 cm), the lid was closed, and the mold was kept in a hot air circulation thermostat at 160° C. for 1 hour.Then, the mold was removed from the thermostatic oven, and the foamed molded product was taken out from the mold.

この発泡成圢䜓は、型䞀杯にシヌトが、発泡し
たものであり、空隙をすべお黄色味を垯びたノボ
ラツク型プノヌル暹脂発泡局が埋め぀くしおは
いるが、郚分的に倧気泡の箇所が存圚したり、極
めお䜎倍率の箇所が存圚する䞍均䞀な成圢䜓であ
぀た。
This foam molded product is a foamed sheet that fills the entire mold, and although all the voids are completely filled with a yellowish novolak type phenolic resin foam layer, there are some areas with large bubbles. The molded product was non-uniform and had areas with extremely low magnification.

因にこの発泡成圢䜓の密床は110Kgm3であ぀
た。
Incidentally, the density of this foamed molded product was 110Kg/m 3 .

(ハ) 発明の効果 この発明の補造法によれば、繊維ずプノヌル
暹脂発泡局ずが均䞀に混圚した耇合発泡䜓局を有
する耇合プノヌル暹脂発泡成圢䜓が効率良く補
造できる板状発泡性耇合䜓を埗るこずができる。
そしおこの板状発泡性耇合䜓によれば予備成圢時
に埓来のごずき暹脂組成物の融点以䞊の加熱凊理
を行なわず、か぀高圧のプレス凊理を必芁ずしな
いため、極めお簡䟿な䜜業で補造でき、しかもず
くに厳密な制埡を行なうこずなく均䞀な耇合プ
ノヌル暹脂発泡成圢䜓を埗るこずができ、工業䞊
極めお有甚な発泡玠材である。
(C) Effects of the Invention According to the production method of the present invention, a plate-shaped foamable composite material can be efficiently produced, which is a composite phenolic resin foam molded product having a composite foam layer in which fibers and a phenolic resin foam layer are evenly mixed. can be obtained.
This plate-like foamable composite does not require heat treatment above the melting point of the conventional resin composition during preforming, and does not require high-pressure press treatment, so it can be manufactured with extremely simple operations. A uniform composite phenolic resin foam molded product can be obtained without particularly strict control, and it is an industrially extremely useful foam material.

【図面の簡単な説明】[Brief explanation of drawings]

第図〜は、この発明の補造方法に係る各
工皋を䟋瀺説明する構成説明図である。   暹脂組成物粉末、′  暹脂組成物、
  綿状シヌト材、  発泡局。
FIGS. 1A to 1D are configuration explanatory diagrams illustrating each process related to the manufacturing method of the present invention. 1...Resin composition powder, 1'...Resin composition,
2... cotton-like sheet material, 3... foam layer.

Claims (1)

【特蚱請求の範囲】[Claims]  プノヌル暹脂初期瞮合物、分解型発泡剀及
び必芁に応じお加えられる硬化剀からなる粉末状
の暹脂組成物を、予め䞊蚘プノヌル暹脂初期瞮
合物ず盞溶性で揮発性の液状物質を含浞させた耇
数の綿状シヌト材の間及び又は該液状物質を含
浞させた綿状シヌト材ず所定の面材ずの間に挟持
させ、䞊蚘暹脂組成物自䜓の溶融枩床未満の枩床
䞋で熱凊理するこずにより、綿状シヌト材内郚に
䞊蚘暹脂組成物が均䞀に含浞されか぀各綿状シヌ
ト材同士及び又は綿状シヌト材ず面材ずが䞀䜓
化された板状の発泡性耇合䜓を埗るこずを特城ず
する板状発泡性耇合䜓の補造法。
1. A powdered resin composition consisting of a phenolic resin initial condensate, a decomposable blowing agent, and a curing agent added as necessary is impregnated in advance with a volatile liquid substance that is compatible with the phenolic resin initial condensate. It is sandwiched between a plurality of cotton-like sheet materials and/or between a cotton-like sheet material impregnated with the liquid substance and a predetermined face material, and heat-treated at a temperature lower than the melting temperature of the resin composition itself. To obtain a plate-shaped foamed composite in which the inside of the cotton-like sheet material is uniformly impregnated with the resin composition and the cotton-like sheet materials are integrated with each other and/or the cotton-like sheet material and the face material. A method for producing a plate-like foamed composite material characterized by:
JP60075765A 1985-04-09 1985-04-09 Preparation of plate-shaped expanded composite Granted JPS61233527A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60075765A JPS61233527A (en) 1985-04-09 1985-04-09 Preparation of plate-shaped expanded composite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60075765A JPS61233527A (en) 1985-04-09 1985-04-09 Preparation of plate-shaped expanded composite

Publications (2)

Publication Number Publication Date
JPS61233527A JPS61233527A (en) 1986-10-17
JPH0333098B2 true JPH0333098B2 (en) 1991-05-15

Family

ID=13585633

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60075765A Granted JPS61233527A (en) 1985-04-09 1985-04-09 Preparation of plate-shaped expanded composite

Country Status (1)

Country Link
JP (1) JPS61233527A (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2791784B2 (en) * 1989-01-26 1998-08-27 豊和繊維工業株匏䌚瀟 Manufacturing method of rigid core material
JPH0418433A (en) * 1990-05-11 1992-01-22 Toray Ind Inc Production of phenol foam and phenol foam
JPH0670150B2 (en) * 1990-06-14 1994-09-07 東レ株匏䌚瀟 Method for producing phenol foam and phenol foam

Also Published As

Publication number Publication date
JPS61233527A (en) 1986-10-17

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