JP5628588B2 - Composition for forming ballpoint pen ink backflow preventer and method for forming ballpoint pen ink backflow preventer - Google Patents
Composition for forming ballpoint pen ink backflow preventer and method for forming ballpoint pen ink backflow preventer Download PDFInfo
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本発明は、ボールペンインキ逆流防止体形成用組成物(以下、単に「逆流防止体形成用組成物」とも称する。)及びボールペンインキ逆流防止体の形成方法(以下、単に「逆流防止体の形成方法」とも称する。)に関し、詳しくは、インキ収容管内に収容されたインキのインキ収容管後端部に接して充填され、筆記により減少するインキに対する追従性に優れ、インキ収容管内壁に付着することなく、収容管内壁のインキ残りを無くすクリーニング性を有する逆流防止体形成用組成物及び逆流防止体の形成方法に関する。 The present invention relates to a composition for forming a ballpoint pen ink backflow preventive body (hereinafter also simply referred to as “composition for forming a backflow preventive body”) and a method for forming a ballpoint pen ink backflow preventive body (hereinafter simply referred to as “method for forming a backflow preventive body”). In detail, the ink contained in the ink containing tube is filled in contact with the rear end portion of the ink containing tube, has excellent followability with respect to the ink reduced by writing, and adheres to the inner wall of the ink containing tube. The present invention also relates to a composition for forming a backflow preventive body having a cleaning property that eliminates ink remaining on the inner wall of the containing tube and a method for forming the backflow preventive body.
ボールペンのインキ収容管内に充填されている逆流防止体形成用組成物は、ペン先を上向きにあるいは横置き状態で長期保管又は運搬した場合に、収容されたインキがインキ収容管後端から漏出することを防止するインキ逆流防止性能、筆記した際のインキ減少に追従して収容管内壁のインキ残りを無くすクリーニング性能、及び、筆記具本体を落下させた時のインキの飛散やインキの流出を防止する耐衝撃性能等が要求される。 The composition for forming a backflow prevention body filled in the ink storage tube of the ballpoint pen leaks out from the rear end of the ink storage tube when the pen tip is stored or transported for a long time with the pen tip facing upward or horizontally. Ink backflow prevention performance to prevent this, cleaning performance to eliminate ink remaining on the inner wall of the receiving tube following ink reduction when writing, and ink scattering and ink outflow when the writing instrument body is dropped Impact resistance performance is required.
従来、かかる逆流防止体形成用組成物としては、ポリブテン、αオレフィン油、精製鉱油、シリコーンオイル等の基油にシリカ粉、金属石けん、ベントナイト、スチレン−ブタジエンエラストマー等の増ちょう剤、及び必要に応じて各種添加剤を配合し、ゲル状物としたものが挙げられる(例えば、特許文献1〜3)。 Conventionally, as a composition for forming such a backflow preventive body, a base oil such as polybutene, α-olefin oil, refined mineral oil, silicone oil, silica powder, metal soap, bentonite, a styrene-butadiene elastomer, and a thickener are necessary. Depending on the case, various additives may be blended to form a gel (for example, Patent Documents 1 to 3).
ところが、これらのゲル状物は、固体であるものの基油と増ちょう剤とを混合したものであるため、強い衝撃を受けた際には容易に変形し、また、高温下での長期保管においては軟化し流出してしまい、いずれにしても完全にインキの漏れを防止する逆流防止体としては機能し得なかった。 However, since these gel-like substances are solids but a mixture of base oil and thickener, they are easily deformed when subjected to strong impacts, and in long-term storage at high temperatures. Was softened and flowed out, and in any case, it could not function as a backflow preventer that completely prevented ink leakage.
これに対し、特許文献4には、強い衝撃による変形や、高温においても軟化することなく形状を保持し得る逆流防止体形成用組成物が開示されている。この逆流防止体形成用組成物は、ハイドロジェン変性オルガノシロキサンとビニル変性ポリシロキサンとの架橋体を用いたものであり、これまでのゲル状物のように単に混合しただけのものでなく高分子材料が架橋反応をしているため、上述のような特性を有し得る。 On the other hand, Patent Document 4 discloses a composition for forming a backflow preventer that can retain its shape without being deformed by a strong impact or softening even at high temperatures. This composition for forming a backflow preventive body uses a crosslinked product of hydrogen-modified organosiloxane and vinyl-modified polysiloxane, and is not simply a mixture like a conventional gel-like material but a polymer. Since the material undergoes a cross-linking reaction, it may have the characteristics as described above.
特許文献4記載の架橋体を用いた逆流防止体は、架橋反応が加熱硬化機構のため、インキ収容管内に充填する前に加熱硬化して架橋体を得る必要がある。しかし、一度硬化した架橋体は容易に変形しないため、インキ収容管への充填が非常に困難であるという問題があった。また、かかる架橋体は粘着性があり、インキ収容管内壁面に付着するため、筆記によるインキ減少に伴う追従性に劣り、クリーニング性にも問題があった。 The backflow preventer using the cross-linked body described in Patent Document 4 needs to obtain a cross-linked body by heating and curing before filling into the ink containing tube because the cross-linking reaction is a heat curing mechanism. However, since the crosslinked body that has been cured once is not easily deformed, there is a problem that it is very difficult to fill the ink containing tube. Moreover, since this crosslinked body has adhesiveness and adheres to the inner wall surface of the ink containing tube, it has poor follow-up properties due to ink reduction by writing, and has a problem in cleaning properties.
そこで本発明の目的は、従来の逆流防止体の課題を解決し、インキ収容管に充填し易く、強い衝撃や高温においても逆流防止体としての形状を保つことができ、且つ、筆記によるインキ減少に伴う追従性にも優れたボールペンインキ逆流防止体形成用組成物および該形成体の形成方法を提供することにある。 Therefore, the object of the present invention is to solve the problems of the conventional backflow preventive body, easily fill the ink containing tube, maintain the shape as the backflow preventive body even under strong impact and high temperature, and reduce ink by writing. Another object of the present invention is to provide a composition for forming a ballpoint pen ink backflow preventive body that is excellent in followability and a method for forming the formed body.
本発明者は、上述した従来の逆流防止体の不具合の解消を図るため、インキ収容管に充填した後の硬化反応により架橋体を形成させるべく鋭意検討した結果、空気中の湿気により硬化反応してシリコーン系架橋体を形成する縮合反応硬化型のシリコーン組成物と炭化水素系離型剤との組み合わせにより上記課題を解決し得ることを見出し、本発明を完成するに至った。 In order to solve the problems of the conventional backflow preventer described above, the present inventors have intensively studied to form a crosslinked body by a curing reaction after filling the ink containing tube, and as a result, the curing reaction is caused by moisture in the air. Thus, the present inventors have found that the above problems can be solved by a combination of a condensation reaction curable silicone composition for forming a silicone-based crosslinked product and a hydrocarbon-based release agent, and have completed the present invention.
すなわち、本発明は、(A)シラノール基末端ポリオルガノシロキサンと、(B)下記一般式〔II〕
R 2 a SiX 4−a 〔II〕
(式中、R 2 は置換または非置換の一価炭化水素基を表し、Xはアルコキシ基を表し、aは1である。)
で表される、分子中に加水分解性基を2個以上含有するシラン化合物及び/又はその部分加水分解縮合物の架橋剤を、前記(A)シラノール基末端ポリオルガノシロキサン100質量部に対して0.1〜20質量部と、(C)硬化触媒と、(D)炭化水素系離型剤と、を含むことを特徴とするボールペンインキ逆流防止体形成用組成物である。
That is, the present invention comprises (A) a silanol group-terminated polyorganosiloxane, (B) the following general formula [II]
R 2 a SiX 4-a [II]
(Wherein R 2 represents a substituted or unsubstituted monovalent hydrocarbon group, X represents an alkoxy group, and a is 1.)
The silane compound containing two or more hydrolyzable groups in the molecule and / or a cross-linking agent of the partial hydrolysis condensate thereof represented by the formula (A) with respect to 100 parts by mass of the silanol group-terminated polyorganosiloxane A composition for forming a ballpoint pen ink backflow preventer comprising 0.1 to 20 parts by mass , (C) a curing catalyst, and (D) a hydrocarbon-based release agent.
本発明において、前記(A)シラノール基末端ポリオルガノシロキサンは、25℃における粘度が100〜500,000cStの範囲であることが好ましい。 In the present invention, the (A) silanol group-terminated polyorganosiloxane preferably has a viscosity at 25 ° C. in the range of 100 to 500,000 cSt.
また、前記(B)の架橋剤は、分子中にアルコキシ基を2個以上含有するアルコキシシラン化合物及び/又はその部分加水分解縮合物であることが好ましい。 The crosslinking agent (B) is preferably an alkoxysilane compound containing two or more alkoxy groups in the molecule and / or a partial hydrolysis condensate thereof.
さらに、前記(C)硬化触媒は、有機スズ化合物であることが好ましい。 Further, the (C) curing catalyst is preferably an organotin compound.
さらにまた、前記(D)炭化水素系離型剤は、25℃における粘度が1〜500,000cStの範囲にある飽和又は不飽和の炭化水素からなる液状物であることが好ましい。 Furthermore, the (D) hydrocarbon release agent is preferably a liquid material composed of saturated or unsaturated hydrocarbons having a viscosity at 25 ° C. in the range of 1 to 500,000 cSt.
また、本発明は、ボールペンのインキ収容管内に収容されたインキの後端部に接触するように、請求項1〜6のうちいずれか一項記載のボールペンインキ逆流防止体形成用組成物を適量充填配置し、次いで縮合硬化反応により架橋させてシリコーン系架橋体を形成させることを特徴とするインキ逆流防止体の形成方法である。 Further, the present invention provides an appropriate amount of the composition for forming a ballpoint pen ink backflow preventive body according to any one of claims 1 to 6 so as to contact the rear end of the ink contained in the ink containing tube of the ballpoint pen. It is a method for forming an ink backflow preventive body characterized in that a silicone-based cross-linked body is formed by filling and arranging and then cross-linking by a condensation curing reaction.
本発明によれば、インキ収容管に充填し易く、強い衝撃や高温においても逆流防止体としての形状を保つことができ、且つ、筆記によるインキ減少に伴う追従性にも優れたボールペンインキ逆流防止体形成用組成物および該形成体の形成方法を提供することができる。 According to the present invention, it is easy to fill an ink containing tube, can maintain a shape as a backflow preventive body even under strong impact or high temperature, and has excellent follow-up characteristics associated with ink reduction by writing. A composition for forming a body and a method for forming the formed body can be provided.
以下、本発明の実施の形態について、詳細に説明する。
本発明の逆流防止体形成用組成物は、(A)シラノール基末端ポリオルガノシロキサンと、(B)分子中に加水分解性基を2個以上含有するシラン化合物及び/又はその部分加水分解縮合物の架橋剤と、(C)硬化触媒と、(D)炭化水素系離型剤と、を含むものである。
Hereinafter, embodiments of the present invention will be described in detail.
The composition for forming a backflow preventer of the present invention comprises (A) a silanol group-terminated polyorganosiloxane, and (B) a silane compound containing two or more hydrolyzable groups in the molecule and / or a partial hydrolysis condensate thereof. A crosslinking agent, (C) a curing catalyst, and (D) a hydrocarbon release agent.
ここで、(A)成分のシラノール基末端ポリオルガノシロキサンは、下記一般式〔I〕で表され、好ましくは25℃の粘度が100〜500,000cStの範囲となる繰り返し単位数nを有する。
(式中、R1は不独立に非置換又は置換の一価の炭化水素基を表す。)
Here, the silanol group-terminated polyorganosiloxane of the component (A) is represented by the following general formula [I], and preferably has a repeating unit number n in which the viscosity at 25 ° C. is in the range of 100 to 500,000 cSt.
(In the formula, R 1 independently represents an unsubstituted or substituted monovalent hydrocarbon group.)
R1としては、好ましくは炭素原子数1〜10、より好ましくは炭素原子数1〜8の炭化水素基であり、例えば、メチル基、エチル基、プロピル基、ブチル基等の低級アルキル基、ビニル基、アリル基、イソプロペニル基等のアルケニル基、アリール基、アラルキル基及びこれらの基の水素原子の一部又は全部がハロゲン原子等で置換された基、例えば、クロロメチル基、トリフロロプロピル基等を挙げることができる。また、これらの一価の炭化水素基R1は、特性上必要な場合には、その一部の水素原子がヒドロキシル基で置換されていてもよい。 R 1 is preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. For example, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, vinyl Groups, allyl groups, alkenyl groups such as isopropenyl groups, aryl groups, aralkyl groups, and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, such as chloromethyl groups, trifluoropropyl groups Etc. In addition, these monovalent hydrocarbon groups R 1 may have some of their hydrogen atoms substituted with hydroxyl groups, if necessary in terms of properties.
R1は、特に好ましくはメチル基、フェニル基、トリフルオロプロピル基であり、さらに特に好ましくは、メチル基である。 R 1 is particularly preferably a methyl group, a phenyl group or a trifluoropropyl group, and more preferably a methyl group.
(B)成分の分子中に加水分解性基を2個以上含有するシラン化合物及び/又はその部分加水分解縮合物の架橋剤は、下式一般式〔II〕で表される。
R2aSiX4−a 〔II〕
(式中、R2は置換または非置換の一価炭化水素基を表し、Xは加水分解性基を表し、aは0または1である。)
The crosslinking agent of the silane compound and / or its partially hydrolyzed condensate containing two or more hydrolyzable groups in the component (B) molecule is represented by the following general formula [II].
R 2 aSiX 4-a [II]
(In the formula, R 2 represents a substituted or unsubstituted monovalent hydrocarbon group, X represents a hydrolyzable group, and a is 0 or 1.)
R2としては、具体的には前記R1と同様のものが例示され、それらの中でもメチル基、エチル基、プロピル基、ブチル基、フェニル基が好ましい。Xの加水分解性基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等のアルコキシ基、メチルエチルケトオキシム基等のケトオキシム基、イソプロペノキシ基等のアルケニルオキシ基、アセトキシ基等のアシロキシ基、ジメチルアミノキシ基等のアミノキシ基が例示され、それらの中でもアルコキシ基が好ましい。 Specific examples of R 2 are the same as those described above for R 1. Among them, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group are preferable. Examples of the hydrolyzable group of X include alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, ketoxime groups such as methylethyl ketoxime group, alkenyloxy groups such as isopropenoxy group, acyloxy groups such as acetoxy group, dimethylamino An aminoxy group such as a xy group is exemplified, and an alkoxy group is preferable among them.
具体的には、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ブチルトリエトキシラン、ビニルトリメトキシシラン、およびこれらの部分加水分解縮合物が例示され、中でもアルキルトリアルコキシシラン類が好ましい。 Specific examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, vinyltrimethoxysilane, and partial hydrolysis condensates thereof. Alkoxysilanes are preferred.
(B)成分の配合量は、(A)成分のシラノール基末端ポリオルガノシロキサン100質量部に対して、好ましくは0.1〜20質量部、より好ましくは1〜10質量部である。(B)成分の配合量が0.1質量部より少ないと架橋点が不十分で硬化が十分に進まず、液状に近い状態のままであるため、逆流防止体の機能であるインキ流出防止効果を良好に得ることができなくなる。一方、20質量部より多いと架橋点が多すぎてしまい、架橋体が目的とするゲル状態よりも硬いものになってしまうため、インキ追従性が不十分となる。 (B) The compounding quantity of a component becomes like this. Preferably it is 0.1-20 mass parts with respect to 100 mass parts of silanol group terminal polyorganosiloxane of (A) component, More preferably, it is 1-10 mass parts. When the blending amount of the component (B) is less than 0.1 parts by mass, the crosslinking point is insufficient, the curing does not proceed sufficiently, and the liquid remains in a liquid state. Cannot be obtained satisfactorily. On the other hand, when the amount is more than 20 parts by mass, there are too many cross-linking points, and the cross-linked product becomes harder than the intended gel state, so that the ink followability becomes insufficient.
(C)成分の硬化触媒とは、シリコーン系架橋体を形成するための架橋反応用触媒であり、好ましくはスズオクトエート、スズカプリレート、スズオレエートのようなカルボン酸金属塩、ジメチルスズジパーサテート、ジブチルスズジパーサテートのような有機スズ化合物が挙げられる。金属スズとして1〜50重量%を含むスズ化合物が硬化触媒として好適に用いられる。また、スズ化合物の硬化触媒以外にもチタン金属を用いたジイソプロポキシビス(アセト酢酸エチル)チタン、ジイソプロポキシビス(アセト酢酸エチル)等の公知の各種チタンキレート化合物が好適に挙げられる。 The component (C) curing catalyst is a catalyst for a crosslinking reaction for forming a silicone-based crosslinked product, preferably a carboxylic acid metal salt such as tin octoate, tin caprylate, tin oleate, or dimethyltin dipersate. And organic tin compounds such as dibutyltin dipersate. A tin compound containing 1 to 50% by weight as metal tin is suitably used as the curing catalyst. In addition to the tin compound curing catalyst, various known titanium chelate compounds such as diisopropoxy bis (ethyl acetoacetate) titanium and diisopropoxy bis (ethyl acetoacetate) using titanium metal are preferably used.
(C)成分の配合量は、(A)成分のシラノール基末端ポリオルガノシロキサン100質量部に対して、好ましくは0.01〜10質量部、より好ましくは0.1〜5質量部であり、さらにより好ましくは0.2〜4質量部である。(C)成分の配合量が0.01質量部より少ないと硬化性が不十分となり粘着性が出てくるため、インキ収容管の内壁に付着して、逆流防止体の追従性が十分ではなくなる。一方、10質量部より多いと硬化性が良すぎてしまい、シリコーン系架橋体が目的とするゲル状態よりも硬いものとなってしまう。さらに、硬化反応が早すぎて、炭素系離型剤がシリコーン系成分から分離して滲み出す前に硬化反応が完了するため、逆流防止体の良好な追従性が得られない。 The amount of component (C) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the silanol group-terminated polyorganosiloxane of component (A). More preferably, it is 0.2-4 mass parts. When the blending amount of the component (C) is less than 0.01 parts by mass, the curability becomes insufficient and the stickiness comes out, so that it adheres to the inner wall of the ink containing tube and the follow-up property of the backflow preventer becomes insufficient. . On the other hand, if the amount is more than 10 parts by mass, the curability is too good and the silicone-based crosslinked product becomes harder than the intended gel state. Furthermore, since the curing reaction is too early and the curing reaction is completed before the carbon-based release agent is separated from the silicone-based component and oozes out, good followability of the backflow preventer cannot be obtained.
(D)成分の炭化水素系離型剤は、好ましくは25℃における粘度が1〜500,000cSt、より好ましくは5cSt〜10,000cStの範囲にある飽和又は不飽和の炭化水素からなる液状物である。(D)成分の炭化水素は、逆流防止体形成用組成物の主成分であるシリコーン系架橋体が硬化反応時及び硬化後にその主成分から分離し、且つその表面に滲み出ることにより、インキ収容管内壁面への付着を防止する効果を本発明の逆流防止体形成用組成物に付与するために配合される。
(D)成分の配合量は、(A)成分のシラノール基末端ポリオルガノシロキサン100質量部に対して、好ましくは.1〜30質量部、より好ましくは5〜20質量部である。(D)成分の配合量が1質量部より少ないと逆流防止体形成用組成物からの(D)成分の分離量が不十分になり、逆流防止体形成用組成物がインキ収容管内壁に付着し、追従性が不十分となる。一方、30質量部より多いと硬化前に分離が始まり、(A)成分のシラノール基末端ポリオルガノシロキサンと分離してしまう。また、硬化後は、逆流防止体形成用組成物からの分離量が多くなり、インキに混入してしまうことがある。
The (D) component hydrocarbon-based mold release agent is preferably a liquid material comprising a saturated or unsaturated hydrocarbon having a viscosity at 25 ° C. of 1 to 500,000 cSt, more preferably 5 cSt to 10,000 cSt. is there. The hydrocarbon of component (D) is contained in the ink when the silicone-based crosslinked body, which is the main component of the composition for forming a backflow preventer, separates from the main component during and after the curing reaction and oozes out to the surface. It mix | blends in order to provide the effect which prevents adhesion to a pipe inner wall surface to the composition for backflow prevention body formation of this invention.
Component (D) is preferably blended in an amount of 100 parts by mass of the silanol group-terminated polyorganosiloxane of component (A). It is 1-30 mass parts, More preferably, it is 5-20 mass parts. If the amount of component (D) is less than 1 part by mass, the amount of component (D) separated from the composition for forming a backflow preventer becomes insufficient, and the composition for forming a backflow preventer adheres to the inner wall of the ink containing tube. However, the followability becomes insufficient. On the other hand, when the amount is more than 30 parts by mass, separation begins before curing, and separation from the silanol group-terminated polyorganosiloxane of component (A) occurs. Moreover, after hardening, the amount of separation from the composition for forming a backflow prevention body increases and may be mixed into the ink.
かかる炭化水素系離型剤の粘度が1cSt未満の場合、粘度が低すぎるため分離性が大きく、硬化後逆流防止剤から分離し、インキの中に混入してしまうおそれがある。一方、500,000cStを超えると分離性が悪くなり、逆流防止体形成用組成物から分離し難いため、逆流防止剤がインキ収容管内壁に付着し、追従性が不十分となる。 When the viscosity of such a hydrocarbon-based release agent is less than 1 cSt, the viscosity is too low, so that the separability is large, and it may be separated from the backflow inhibitor after curing and mixed into the ink. On the other hand, if it exceeds 500,000 cSt, the separability deteriorates and it is difficult to separate from the composition for forming a backflow preventer, so that the backflow preventive agent adheres to the inner wall of the ink containing tube and the followability becomes insufficient.
(D)成分の炭化水素系離型剤としては、一般式がCnH2n+2で表される常温で液状のアルケン、具体的には、ホワイト油、白色鉱油、水パラフィン、ミネラルオイル、ミネラルオイルホワイト、医療用パラフィン等が挙げられる。また、不飽和基を持つオレフィンから合成されるポリオレフィンであるポリ−α−オレフィン、エチレンとαオレフィンの反応物やポリフテン等であってもよい。 Component (D) is a hydrocarbon-based mold release agent having a general formula of C n H 2n + 2, which is a liquid alkene at room temperature, specifically, white oil, white mineral oil, water paraffin, mineral oil, mineral oil. Examples thereof include white and medical paraffin. Further, it may be a poly-α-olefin, which is a polyolefin synthesized from an olefin having an unsaturated group, a reaction product of ethylene and α-olefin, polyphten, or the like.
本発明においては、上述した成分(A)〜(D)以外にも本発明の目的を損なわない範囲において、組成物の特性を向上させるために種々の添加剤を配合することができる。例えば、組成物の流動性をコントロールするために、25℃における粘度が100〜500,000cStの範囲であるジメチルポリシロキサン、メチルフェニルポリシロキサン等のシリコーンオイル、又は、ヒュームドシリカ、沈殿シリカ成及びそれらを疎水処理した物等を配合できる。また、充填剤又は増量剤等として石英粉、溶融石英、球状シリカ、ケイソウ土、ゼオライト、炭酸カルシウム、二酸化チタン、酸化鉄、アルミナ、水酸化アルミナ等を配合できる。さらに、必要に応じて着色するために各種着色剤も配合できる。硬化性を促進させるために、水、又はメタノール、エタノール、プロパノール、メチルセルソルブ等のアルコール類を添加することも任意である。 In the present invention, in addition to the components (A) to (D) described above, various additives can be blended in order to improve the properties of the composition as long as the object of the present invention is not impaired. For example, in order to control the fluidity of the composition, silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane having a viscosity at 25 ° C. in the range of 100 to 500,000 cSt, or fumed silica, precipitated silica and The thing etc. which hydrophobized them can be mix | blended. Further, quartz powder, fused quartz, spherical silica, diatomaceous earth, zeolite, calcium carbonate, titanium dioxide, iron oxide, alumina, alumina hydroxide, etc. can be blended as fillers or extenders. Further, various colorants can be blended for coloring as required. In order to promote curability, it is optional to add water or alcohols such as methanol, ethanol, propanol, and methyl cellosolve.
本発明の逆流防止体形成用組成物は、例えば、プラネタリーミキサー、万能混練器、トリミックス等の混合器を用いて、均一に混合して得られる。得られた混合物は、常温で湿度50%の環境下で少なくとも24時間放置することにより、所望の架橋体を良好に得ることができる。更に、厚さ10mm以上に完全に硬化させるためには、48時間以上放置する必要がある。 The composition for forming a backflow prevention body of the present invention can be obtained by, for example, uniformly mixing using a mixer such as a planetary mixer, a universal kneader, or a trimix. The obtained mixture can be satisfactorily obtained in a desired cross-linked form by allowing it to stand at room temperature in an environment of 50% humidity for at least 24 hours. Further, in order to completely cure to a thickness of 10 mm or more, it is necessary to leave it for 48 hours or more.
以下において実施例をあげ、本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、実施例中、部とあるのはいずれも質量部、粘度とあるのは25℃における動粘度を表す。 Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples. In Examples, “part” means “part by mass” and “viscosity” means kinematic viscosity at 25 ° C.
実施例1
両末端がシラノール基で封止されたジメチルポリシロキサン(粘度:3,000cSt)100部と、メチルトリエトシシラン5部と、ジメチルポリシロキサン(粘度:3,000cSt)50部とを良く混合し、さらに流動パラフィン(40℃における粘度が40cSt)10部を配合し、均一になるまで良く混合した。その後、ジオクチルスズアセチルアセテート1部を加え、良く混合後、脱泡処理を行い、実施例1の逆流防止体形成用組成物を得た。
Example 1
100 parts of dimethylpolysiloxane (viscosity: 3,000 cSt) sealed at both ends with silanol groups, 5 parts of methyltriethoxysilane, and 50 parts of dimethylpolysiloxane (viscosity: 3,000 cSt) are mixed well. Further, 10 parts of liquid paraffin (viscosity at 40 ° C. of 40 cSt) was blended and mixed well until uniform. Thereafter, 1 part of dioctyltin acetylacetate was added, and after mixing well, defoaming treatment was performed to obtain a composition for forming a backflow preventer of Example 1.
実施例2
離型剤の流動パラフィンの分離防止と、インキ収容管への充填直後にインキ収容管が斜めに保管された場合の流出防止とのために、脱泡処理の前に、BET法による比表面積が200m2の微粉末シリカ粉を4部配合した以外は実施例1と同様にして、実施例2の逆流防止体形成用組成物を得た。
Example 2
In order to prevent separation of liquid paraffin as a release agent and to prevent outflow when the ink storage tube is stored obliquely immediately after filling the ink storage tube, the specific surface area by the BET method is increased before the defoaming treatment. A backflow prevention body-forming composition of Example 2 was obtained in the same manner as in Example 1 except that 4 parts of 200 m 2 of finely divided silica powder were blended.
比較例1
ジメチルポリシロキサン(粘度:3,000cSt)100部に、BET法による比表面積が200m2の微粉末シリカ粉に疎水処理したシリカ粉8部を配合し、3本ロールにて均一に混合後、脱泡処理を行い、比較例1としての逆流防止体形成用組成物を得た。
Comparative Example 1
Compound 100 parts of dimethylpolysiloxane (viscosity: 3,000 cSt) is mixed with 8 parts of silica powder hydrophobized to fine powder silica powder having a specific surface area of 200 m 2 by BET method. Foam treatment was performed to obtain a composition for forming a backflow preventer as Comparative Example 1.
比較例2
ジメチルポリシロキサン(粘度:3,000cSt)100部に、BET法による比表面積が200m2の微粉末シリカ粉に疎水処理したシリカ粉5部を配合し、3本ロールにて均一に混合後、脱泡処理を行い、比較例2としての逆流防止体形成用組成物を得た。
Comparative Example 2
100 parts of dimethylpolysiloxane (viscosity: 3,000 cSt) is blended with 5 parts of silica powder hydrophobized to fine powder silica powder having a specific surface area of 200 m 2 according to the BET method. Foam treatment was performed to obtain a composition for forming a backflow preventer as Comparative Example 2.
比較例3
100℃における粘度が100cStのエチレン−α−オレフィンコポリマー100部に、BET法による比表面積が200m2の微粉末シリカ粉に疎水処理したシリカ粉5部を配合し、3本ロールにて均一に混合後、脱泡処理を行い、比較例3としての逆流防止体形成用組成物を得た。
Comparative Example 3
Blend 100 parts of ethylene-α-olefin copolymer with a viscosity of 100 cSt at 100 ° C and 5 parts of silica powder hydrophobized into fine silica powder with a specific surface area of 200 m 2 by BET method, and mix evenly with 3 rolls. Then, the defoaming process was performed and the composition for backflow prevention body formation as the comparative example 3 was obtained.
比較例4
100℃における粘度が6cStのα−オレフィンコポリマー100部に、12ヒドロキシステアリン酸リチウム5部を配合し、加熱溶解後、冷却し、3本ロールにて均一に混合撹拌し、脱泡処理を行い、比較例4としての逆流防止体形成用組成物を得た。
Comparative Example 4
5 parts of 12 hydroxy lithium stearate is blended with 100 parts of an α-olefin copolymer having a viscosity at 100 ° C. of 6 cSt, dissolved by heating, cooled, uniformly mixed and stirred with three rolls, and defoamed. A composition for forming a backflow preventer as Comparative Example 4 was obtained.
比較例5
両末端がビニル基で封止されたジメチルポリシロキサンとハイドロジェン基を有するジメチルポリシロキサンに白金触媒を配合した市販のシリコーンゲルTSE3062を用いた。モメンチィブ社製商品名TSE3062(A)50部とTSE3062(B)50部とを良く混合後、脱泡処理を行ない、50℃にて24時間過熱硬化させて、比較例5としての逆流防止体形成用組成物を得た。尚、150℃であれば、1時間で硬化した。
Comparative Example 5
A commercially available silicone gel TSE3062 in which a platinum catalyst was blended with dimethylpolysiloxane having both ends sealed with vinyl groups and dimethylpolysiloxane having a hydrogen group was used. After mixing 50 parts of TSE3062 (A) trade name and 50 parts of TSE3062 (B) well by Momentive Co., defoaming treatment was performed, followed by overheating at 50 ° C. for 24 hours to form a backflow preventive body as Comparative Example 5. A composition was obtained. In addition, when it was 150 degreeC, it hardened | cured in 1 hour.
比較例6
両末端がシラノール基で封止されたジメチルポリシロキサン(粘度:3,000cSt)100部とメチルトリエトシシラン5部、ジメチルポリシロキサン(粘度:3,000cSt)50部を混合し、均一になるまで良く混合した。その後、ジオクチルスズアセチルアセテート1部を加え、良く混合後、脱泡処理を行い、比較例6としての逆流防止体形成用組成物を得た。
Comparative Example 6
Mix 100 parts of dimethylpolysiloxane (viscosity: 3,000 cSt) sealed at both ends with silanol groups, 5 parts of methyltriethoxysilane, and 50 parts of dimethylpolysiloxane (viscosity: 3,000 cSt) until uniform. Mix well. Thereafter, 1 part of dioctyltin acetylacetate was added, and after mixing well, defoaming treatment was performed to obtain a composition for forming a backflow preventer as Comparative Example 6.
性能試験
先端に0.7mmのボールを付けたステンレス製ボールペンチップの付いた内径3.8mmのポリプロピレン製インキ収容管に、一般的なボールペン用水性インキを注入し、このインキの後端部に接触するように、前記実施例1〜2及び比較例1〜6の逆流防止体形成用組成物をインキとの界面から15mmの高さになるようにそれぞれ充填配置し、下記に示す各種試験を行った。
なお、実施例1及び実施例2の逆流防止体形成用組成物はインキ収容管に充填後常温にて24時間放置し、縮合硬化反応によりシリコーン架橋体を形成させて、各種試験に供した。
Performance test Water-based ink for ballpoint pens is injected into a polypropylene ink storage tube with an internal diameter of 3.8 mm with a stainless steel ballpoint pen tip with a 0.7 mm ball at the tip, and contacts the rear end of this ink. Thus, the backflow preventive body forming compositions of Examples 1 and 2 and Comparative Examples 1 to 6 were filled and arranged so as to be 15 mm from the interface with the ink, and various tests shown below were conducted. It was.
The compositions for forming a backflow preventive body of Example 1 and Example 2 were filled in an ink containing tube and allowed to stand at room temperature for 24 hours to form a silicone cross-linked body by condensation curing reaction and used for various tests.
(インキ追従性試験)
約40cm/秒の速度にて筆記を行い、インキの消耗に伴い逆流防止体が追従するか否かを観察した。逆流防止体が、インキの消費に伴い良好に追従し、正常に筆記できるものを合格(○)とし、追従に乏しく、部分的に筆跡が形成できないものを不良(△)及び、全く筆跡が形成できないものを不合格(×)とした。
(Ink followability test)
Writing was performed at a speed of about 40 cm / second, and it was observed whether or not the backflow prevention body followed as the ink was consumed. A backflow preventer that follows well with ink consumption and that can be written normally is judged as acceptable (○), and poorly tracked and partially unable to form handwriting. Those that could not be evaluated were rejected (x).
(ビジブル性試験)
前記インキ追従性試験後、インキがインキ収容管の約半分の位置まで減少した時点のインキ収容管内壁に付着したインキと逆流防止体の状態を目視にて観察した。インキ収容管内壁面にインキや逆流防止体が付着していないものを合格(○)とし、インキ及び逆流防止体の一部が付着しているものを不合格(×)とした。
(Visibility test)
After the ink follow-up test, the state of the ink adhering to the inner wall of the ink containing tube and the state of the backflow preventer was visually observed when the ink decreased to about half the position of the ink containing tube. The case where the ink and the backflow preventive body were not attached to the inner wall surface of the ink containing tube was evaluated as acceptable (◯), and the case where the ink and a part of the backflow preventive body were adhered was determined as unacceptable (x).
(1日経過後のインキ追従性試験)
室温にて1日放置した後、約40cm/秒の速度にて筆記を行い、インキの消耗に伴い逆流防止体が追従するか否かを観察した。逆流防止体が、インキの消費に伴い良好に追従し、正常に筆記できるものを合格(○)とし、追従に乏しく、部分的及び全く筆跡が形成できないものを不合格(×)とした。
(Ink following test after 1 day)
After being allowed to stand at room temperature for 1 day, writing was performed at a speed of about 40 cm / second, and it was observed whether the backflow preventer would follow as the ink was consumed. A backflow preventer that satisfactorily followed as the ink was consumed and was able to write normally was evaluated as pass (◯), and a sample that was poorly tracked and could not be partially or completely formed was rejected (x).
(1日経過後のビジブル性試験)
前記1日経過後のインキ追従性試験後、インキがインキ収容管の約半分の位置まで減少した時点のインキ収容管内壁に付着したインキと逆流防止体の状態を目視にて観察した。インキ収容管内壁面にインキや逆流防止体が付着していないものを合格(○)とし、インキ及び逆流防止体の一部が付着しているものを不合格(×)とした。
(Visibility test after 1 day)
After the ink follow-up test after 1 day, the state of the ink adhering to the inner wall of the ink containing tube and the state of the backflow preventer when the ink decreased to about half the position of the ink containing tube was visually observed. The case where the ink and the backflow preventive body were not attached to the inner wall surface of the ink containing tube was evaluated as acceptable (◯), and the case where the ink and a part of the backflow preventive body were adhered was determined as unacceptable (x).
(耐衝撃性試験)
ペン先を上に手で持ち、高さ1mの高さからコンクリート製床面に10回落下させた後、インキ及び逆流防止体の状態を目視にて観察した。インキの一部が逆流防止体の中に、その逆にインキの中に逆流防止体の一部の移動が観察されたものを不合格(×)とし、これらの現象が観察されないものを合格(○)とした。
(Impact resistance test)
After holding the pen tip by hand and dropping it 10 times from a height of 1 m onto the concrete floor, the state of the ink and the backflow preventer was visually observed. A part of the ink in the backflow preventive body, conversely, a part of the backflow preventive body that was observed to move in the ink was rejected (x), and a case in which these phenomena were not observed passed ( ○).
(分離性試験)
ペン先をキャップでシールし、正立状態で50℃の恒温槽に1ヶ月放置した後、逆流防止体の状態を目視にて観察した。初期と比較して、オイルの分離や状態の変化の無いものを合格(○)とし、オイルの分離または状態の変化が生じたものを不合格(×)とした。
(Separability test)
The nib was sealed with a cap and left standing in a constant temperature bath at 50 ° C. for one month, and the state of the backflow preventer was visually observed. In comparison with the initial stage, a case where there was no oil separation or a change in state was determined as pass (◯), and a case where oil separation or a change in state occurred was determined as failure (x).
(1ヵ月経時後のインキ追従性試験)
50℃の恒温槽に1ヶ月放置した後、約40cm/秒の速度にて筆記を行い、インキの消耗に伴い逆流防止体が追従するか否かを観察した。逆流防止体が、インキの消費に伴い良好に追従し、正常に筆記できるものを合格(○)とし、追従に乏しく、部分的及び全く筆跡が形成できないものを不合格(×)とした。
(Ink follow-up test after 1 month)
After being left in a thermostatic bath at 50 ° C. for one month, writing was performed at a speed of about 40 cm / second, and it was observed whether the backflow preventer followed up with ink consumption. A backflow preventer that satisfactorily followed as the ink was consumed and was able to write normally was evaluated as pass (◯), and a sample that was poorly tracked and could not be partially or completely formed was rejected (x).
性能試験の結果を下記の表1に示す。 The results of the performance test are shown in Table 1 below.
Claims (7)
(A)シラノール基末端ポリオルガノシロキサンと、
(B)下記一般式〔II〕
R 2 a SiX 4−a 〔II〕
(式中、R 2 は置換または非置換の一価炭化水素基を表し、Xはアルコキシ基を表し、aは1である。)
で表される、分子中に加水分解性基を2個以上含有するシラン化合物及び/又はその部分加水分解縮合物の架橋剤を、前記(A)シラノール基末端ポリオルガノシロキサン100質量部に対して0.1〜20質量部と、
(C)硬化触媒と、
(D)炭化水素系離型剤と、
を含むことを特徴とするボールペンインキ逆流防止体形成用組成物。 In the composition for forming a ballpoint ink backflow preventer that is filled in the rear end of the ink stored in the ink storage tube and follows as the ink is consumed.
(A) a silanol group-terminated polyorganosiloxane;
(B) The following general formula [II]
R 2 a SiX 4-a [II]
(Wherein R 2 represents a substituted or unsubstituted monovalent hydrocarbon group, X represents an alkoxy group, and a is 1.)
The silane compound containing two or more hydrolyzable groups in the molecule and / or a cross-linking agent of the partial hydrolysis condensate thereof represented by the formula (A) with respect to 100 parts by mass of the silanol group-terminated polyorganosiloxane 0.1 to 20 parts by mass ;
(C) a curing catalyst;
(D) a hydrocarbon release agent;
A composition for forming a ballpoint ink backflow preventive body, comprising:
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